CN105056773B - The preparation method of the embedded hollow composite membrane of enhancing in original position - Google Patents
The preparation method of the embedded hollow composite membrane of enhancing in original position Download PDFInfo
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Abstract
Prepared the present invention relates to separation membrane material and enhancing modification technology, it is desirable to provide a kind of preparation method of the embedded hollow composite membrane of enhancing in situ.Including：It will obtain coating feed liquid after the mixing of fluoropolymer resin, pore-foaming agent, hydrophilizing agent and solvent, stirring, filtering, vacuum defoamation；By the smooth cross winding of multi-strand yarns on the plug of rotation, yarn crossovers point is bonded with ultra-sonic welded, is formed after network tubrOar enhancing base materials, is moved down along plug and continuously enter coating head；Coating feed liquid penetrates into yarn and coats enhancing base materials completely, leaves continuously from coating head and enters after coagulating bath, surface feed liquid and the water coke slurry film forming in coagulating bath, final that the embedded hollow composite membrane of enhancing in situ is made.The preparation method of the present invention is simple, continuous, and can realize industrialized production；Peeling is not present in the present invention, the problem of overcoming the peel strength deficiency of composite membrane in the prior art；The embedded network tubrOar enhancing base materials cost in original position is relatively low, final reduction membrane material cost.
Description
Technical field
Prepared the invention belongs to separation membrane material and enhancing technical field of modification, the present invention relates to a kind of embedded enhancing in situ
The preparation method of hollow composite membrane.
Background technology
At present, polymer separation film as a kind of important separation material have been widely used sewage disposal, medicine, beverage,
The fields such as chemical industry, electronics, food and papermaking.Hollow-fibre membrane has big specific surface area, filling density height, small volume, processing effect
High and simple production process the advantage of rate, is a kind of main membrane material.In order that cross-film resistance is low, the wall thickness of hollow-fibre membrane
General relatively thin (about tens microns), although hollow-fibre membrane, which belongs to self-cradling type membrane material, has certain mechanical strength, but by
It is high voidage loose structure in polymer separation film membranous wall, is still suffered from when applied to high-pressure fluid processing or dither
The not enough shortcoming of mechanical strength.In order to improve the mechanical strength of hollow fibre polymeric membranes, Canadian Zenon companies (US
The A1 of Patent No.5,472,607, US2003/0098275A1, WO 00/78437) make public for the first time a kind of compound polymerization
The technology of preparing of thing hollow-fibre membrane, the polymer composite hollow fiber membrane prepared by the technology only has very thin one layer of polymeric
Separating layer, its thickness is 0.01~0.1mm, therefore the water flux of resulting film greatly increases, and transmembrane pressure is substantially reduced.But
It is that the hollow-fibre membrane is the outer surface that polymer separation film is compounded in the fiber braided tube woven in advance, therefore is polymerize
Binding ability between thing seperation film and fiber braided tube is bad, during reverse cleaning is carried out to film, polymer separation film
Easily fallen off between fiber braided tube.Kolon Industrial Co., Ltd of South Korea (US2008/0292823A1, US2008/
0305290A1, WO 2008/097011A1) disclose a kind of speed of travel by adjusting fiber braided tube and casting solution extrusion
The ratio of amount controls the technology of casting solution infiltration capacity.By the technology can by the control of the infiltration capacity of casting solution 30% with
Interior, resulting composite hollow fibre microporous barrier has thickness less than 0.2mm one layer of polymeric seperation film.Chinese patent
CN100546702C discloses the coating casting solution on capillary braid and prepares composite membrane, coating liquid is penetrated into braid
It is interior to improve compound film strength.Chinese patent CN101357303B and CN102784566B disclose modified painting first pre- to woven tube
Cover, then secondary coating preparation liquid prepares composite membrane.Although the similar techniques strengthen seperation film and compiled with fiber to a certain extent
Knit the adhesion between pipe, but without thoroughly solve composite hollow fibre microporous barrier in backwash process polymer separation film with
The problem of fiber braided tube departs from.Above-mentioned method typically all first prepares pipe-type woven pipe, is then coated with casting solution
Composite membrane is prepared, process gap is simultaneously relative complex.The braiding speed of tubular braid is slower, probably prepares composite membrane speed
1/10, it is necessary to more braider.In order to which the rigidity and circularity of tubular braid need the certain thickness of woven tube to ensure, phase
Correspondence prepare all the increase of composite membrane wall thickness, hollow-fibre membrane high packed density relatively preferably less external diameter, so again
The internal diameter for closing film is corresponding just smaller, limits the length available of the hollow-fibre membrane in encapsulation membrane module.Further, pipe-type woven
Thing raw material and manufacturing cost are higher, improve the cost of composite membrane.
Chinese patent CN101543731B discloses a kind of fiber braided tube embedded enhanced type polymer doughnut micropore
The preparation method of film, it is characterised in that employ the integrated film-forming process of fibrage-coextrusion, i.e., core liquid pipe is fixed on volume
Knit in the middle of pipe, while fibre bundle is turned into fiber braided tube along the braiding of core liquid pipe, then by casting solution, core liquid, fiber braided tube
It is coextruded by extrusion die, and it is micro- by phase transition method to prepare fiber braided tube embedded enhanced type polymer doughnut
Pore membrane.Fiber braided tube is successfully embedded in the body of hollow-fibre membrane by this method, and core liquid is incorporated into woven tube
Inner chamber, has efficiently controlled the internal diameter of hollow-fibre membrane, so as to solve in the enhancing of conventional application processes for forming cellulose woven tube
Hollow fiber film middle polymeric layer easily departs from braided fiber pipe, the hollow fiber cavity easily technical barrier such as blocking, but this method is deposited
It is slower in fibrage speed, limit the industrialization difficult to realize of film efficiency.Chinese patent CN100393397C and
CN101837248B, which discloses first to prepare, winds fiber networking or the secondary painting of adhering fibre silk on hollow-fibre membrane, then outer surface
Cover preparation liquid and prepare composite membrane, it is difficult control that such method, which is prepared relative complex,.
The content of the invention
The technical problem to be solved in the present invention is to overcome peel strength deficiency, the industrialization of composite membrane in the prior art
The problem of production difficulty and higher membrane material cost, there is provided a kind of preparation method of the embedded hollow composite membrane of enhancing in situ.
To achieve these goals, the technical solution adopted by the present invention is as follows：
A kind of preparation method of the embedded hollow composite membrane of enhancing in situ is provided, comprised the steps：
(1) by fluoropolymer resin, pore-foaming agent, hydrophilizing agent and solvent according to 15~20: 5~20: 1~5: 55~79 weight
Than mixing, then stir, obtain coating feed liquid after filtering, vacuum defoamation；
(2) by multi-strand yarns along the smooth cross winding of guide groove on the plug of rotation, the crosspoint of yarn is with ultrasonic bond
Bonding is connect, the network tubrOar enhancing base materials being wrapped on plug are formed；
(3) it is continuously supplied to measuring pump by feed liquid is coated in hollow coating head, network tubrOar is increased using tractive force
Strong basis material moves down along plug and continuously enters coating head；Coating feed liquid is penetrated into yarn and cladding network tubrOar completely increases
While strong basis material, the plug of rotation is scraped as scraper in network tubrOar enhancing base materials inner surface makes coat；
(5) under tractive force effect, the network tubrOar enhancing base materials for being applied feed liquid cladding leave continuously from coating head entrance
Coagulating bath, surface feed liquid and the water coke slurry film forming in coagulating bath of network tubrOar enhancing base materials are final that embedded enhancing in situ is made
Hollow composite membrane.
In the present invention, described fluoropolymer resin is polyether sulfone, modified poly (ether-sulfone), Kynoar, polysulfones, polychlorostyrene second
One or two kinds of in alkene, polyacrylonitrile or cellulose acetate.
In the present invention, described pore-foaming agent is polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, ethylene glycol, diethylene glycol (DEG)
Or two kinds of triethylene glycol or three kinds.
In the present invention, described hydrophilizing agent is sulfonated polyether sulfone, polymethyl methacrylate, PULLRONIC F68
One kind of block copolymer or polyether silicone.
In the present invention, described solvent is DMA, DMF, N- crassitudes
One or both of ketone, dimethyl sulfoxide (DMSO), trimethyl phosphate or triethyl phosphate.
In the present invention, described yarn is the composite filament of denier 200~1000, and its material is polypropylene, polyester or nylon
In one kind.
In the present invention, described network tubrOar enhancing base materials are welded by 4~32 stock yarn line cross windings, its internal diameter
For 1~12mm, external diameter is mesh aperture between 1.6~20mm, yarn in 0.1~2mm.
In the present invention, when plug external diameter is more than 3mm, plug uses hollow tubular structure；Core is introduced by its upper end
Liquid, makes core liquid along trickling downwards inside plug；After network tubrOar enhancing base materials complete coating in coating head, drawn from core
The end of rod departs from；Core liquid flows out from the bottom of plug, and is carried out with the surface of coat on the inside of network tubrOar enhancing base materials
Solvent is exchanged, and realizes solidification；
The core liquid refers to one kind in water, DMA, DMF or triethyl phosphate
Or two kinds of mixed liquors；
When plug external diameter is less than 3mm, core liquid is not introduced, network tubrOar enhancing base materials are wrapped up using only coating material.
In the present invention, the obtained embedded enhancing for strengthening hollow composite membrane in situ is to prepare composite membrane with network structure
During be formed in situ；The internal diameter of the embedded hollow composite membrane of enhancing in situ is 1~12mm, and external diameter is 1.6~20mm, is put down
Equal aperture is 0.01~1 micron.
In the present invention, the stirring described in step (1) refers to persistently stir at 80 DEG C 12 hours.
Using the embedded hollow composite membrane product of enhancing in situ made from the method for the invention, such as composite membrane internal diameter is in 1-
2mm, external diameter is hollow-fibre membrane in 1.6-3mm, and predominant package is that (membrane type is biological anti-applied to immersion MBR for external-compression type component
Answer device)；Such as internal diameter is tubular membrane in 3-20mm in 2-12mm, external diameter, and predominant package is that inner pressed is applied to percolate, contained
The processing of the high-solids content liquid material such as sewage, fruit juice of activated sludge.When plug external diameter is more than 3mm, hollow rigid can be used
Pipe；When plug external diameter is less than 3mm, solid, rigid rod can be used, the technique using addition core liquid is now just not required to.
Compared with prior art, the beneficial effects of the present invention are：
(1) preparation method is simple, continuous, and can realize industrialized production；
(2) peeling is not present in the present invention, the problem of overcoming the peel strength deficiency of composite membrane in the prior art；
(3) embedded network tubrOar enhancing base materials cost in situ is relatively low, final reduction membrane material cost.
Brief description of the drawings
Fig. 1 is the embedded hollow composite membrane preparation technology schematic flow sheet of enhancing in situ.
Fig. 2 is the embedded hollow composite membrane Preparation equipment schematic diagram of enhancing in situ.
In figure：Coat feed liquid dissolving tank 1, coating material metering and conveying device 2, coating feed liquid 21, yarn actinobacillus device 3, yarn
Line ureeling barrel 31, yarn unwrapping wire rotary system 32, core flow container 4, core liquid metering and conveying device 5, core liquid pipe 51, plug 6, plug rotation
Rotary device 7, rotary system 71, Mandrel Rotating connector 72, swivel joint 8, ultrasonic welding device 9, ultrasonic generator 91, ultrasound
Plumb joint 92, plug fixing device 10, coating first 11, gel water bath 12, spiral filament forming machine 13, the hollow composite membrane 14 of enhancing.
Embodiment
Below in conjunction with the accompanying drawings, embodiments of the present invention are described in detail.
Statement is needed first, and the device of the preparation the being described below embedded hollow composite membrane of enhancing in situ, is only the present invention
Content for example, it is impossible to which equipment realization can only be relied on by being considered as the present invention.Therefore, the explanation about equipment is not construed as
It is the technology restriction to the present invention.Those skilled in the art are after implementation method of the present invention is understood, the skill that can be grasped by it
The design or manufacture of equipment can be carried out.
In the present embodiment, preparing the device of the embedded hollow composite membrane of enhancing in situ includes gel water bath 12 and spiral filament forming machine
13, and application system, yarn actinobacillus device and feed liquid induction system；Wherein,
Application system includes plug 6, ultrasonic welding device 9, plug fixing device 10 and coating first 11.
Plug 6 is stainless steel hollow tube or solid tubes, and external diameter is 1.5~12mm, preferably greater than 3mm hollow tubes.On plug 6
End outer surface is uniformly distributed the groove of shape of threads as yarn guide groove, and it sets purpose to be that multi-strand yarns are handed over along guide groove is smooth
Fork is wrapped on the plug of rotation.
Plug 6 is suspended from the top of gel water bath 12 vertically, and the upper end of plug 6 passes through Mandrel Rotating connector 72, rotation
Adapter 8 realizes and is connected that Mandrel Rotating connector 72 then connects with rotary system 71 with core liquid pipe 51.
Plug 6 sequentially passes through downwards ultrasonic welding device 9, plug fixing device 10 and coating first 11；Ultrasonic welding device 9
Including ultrasonic generator 91 and ultrasonic bond joint 92.Spacing is kept between plug fixing device 10 and plug 6, makes plug 6 in quilt
The axle center rotation around itself can be realized while fixed.Coating first 11 is hollow structure, and its inner space is measured with coating material
The output pipe of conveying device 1 is connected；The plug 6 is from top to bottom through the inner space of coating first 11.
Yarn actinobacillus device includes yarn ureeling barrel 31 and yarn unwrapping wire rotary system 32, and the quantity of yarn actinobacillus device can
To be 1~8 group.At least 2 yarn ureeling barrels 31 of every group of yarn actinobacillus device, and it is divided into the both sides on the top of plug 6；
Feed liquid induction system includes coating feed liquid dissolving tank 1 and core flow container 4, and the tank bottom of coating feed liquid dissolving tank 1 passes through pipe
Road and coating material metering and conveying device 2 are connected to coating first 11, and the tank bottom of core flow container 4 passes through pipeline and core liquid metering and conveying device 5
It is connected to core liquid pipe 51.Coating material metering and conveying device 2 and core liquid metering and conveying device 5 can use measuring pump.
The realization principle of the present invention：
Core liquid is delivered to after core liquid pipe 51 by core liquid metering and conveying device 5, rotated joint 8, the edge of Mandrel Rotating connector 72
Trickle downwards the hollow inside of plug 6.Rotary system 71 drives Mandrel Rotating connector 72, makes plug 6 around the axis of its own
Rotate (core liquid pipe 51 and swivel joint 8 are fixed).The smooth cross winding of yarn on multiple yarn ureeling barrels 31 is in rotation
Plug outer surface, bonding is welded in its crosspoint by ultrasonic welding device 9, so as to form network tubrOar enhancing base materials.Before this
The network tubrOar enhancing base materials of welding are completed under the traction of spiral filament forming machine 13, it is constantly descending and coat after feed liquid final along plug 6
Departed from by bottom.Coating feed liquid is transported to coating first 11 by coating material metering and conveying device 2 and fills up its cavity, works as network
Tubulose enhancing base materials are when continuing to pass through coating first 11, and coatings feed liquid penetrates into yarn and complete wetting cladding network tubrOar increases
Strong basis material.The plug 6 of rotation forms certain thickness coating as scraper in the inner surface striking of network tubrOar enhancing base materials
Layer.Then, the inner surface of core liquid and coat is exchanged and solidified, outermost feed liquid in the bottom progress solvent of plug 6
Continue to be exchanged into film in gel water bath 12 is entered.
In the present invention, when the external diameter of plug 6 is more than 3mm, plug 6 uses hollow tubular structure；Introduce core liquid solidification work
Skill；When the external diameter of plug 6 is less than 3mm, core liquid is not introduced, network tubrOar enhancing base materials are wrapped up using only coating material.
Embodiment 1：
By weight percentage by 20% polyethersulfone resin (BASF 6020P), 55%N, dinethylformamide, 11% gather
Ethylene glycol 200,9% PVP K-30 and 5% sulfonated polyether sulfone are added in agitator tank, are stirred 12 hours at 80 DEG C,
Filtering, vacuum defoamation obtain coating feed liquid.The polyester conjugated yam of 8 deniers 750 is oriented to smooth by the plug of rotation respectively
Cross winding is on the external diameter 4mm hollow plug of stainless steel, and crosspoint ultra-sonic welded is bonded to network tubrOar base material.In tractive force
Effect lower network tubular substrate continuously enters coating head, while coat feed liquid is pumped into coating head by metering.Coat feed liquid
Yarn and complete wetting cladding network tubular substrate are penetrated into, the network tubrOar base material for being applied feed liquid cladding leaves continuously from coating
Head, the plug of rotation is as scraper in the certain thickness coat of tubular substrate inner surface striking, and core liquid (water) enters with coat
Row solvent is exchanged and solidified, and outer surface feed liquid enters coagulating bath and exchanges film forming, 0.02 micron of the average pore size of film, and internal diameter is
4mm, external diameter is 6mm, and the pure water internal pressure flux under the conditions of 0.2MPa, 25 DEG C is 740L/m2 .h。
Embodiment 2：
20% polyethersulfone resin (BASF 6020P), 50%N, N- dimethyl acetamides, 20% phosphoric acid by weight percentage
Trimethyl, 6% polyethylene glycol 200,3% PVP K-30 and 1% sulfonated polyether sulfone are added in agitator tank, at 80 DEG C
Stirring 12 hours, filtering, vacuum defoamation obtain coating feed liquid.The polyester conjugated yam of 8 deniers 750 passes through the core of rotation respectively
Rod is oriented to smooth cross winding on the external diameter 4mm hollow plug of stainless steel, and crosspoint ultra-sonic welded is bonded to network tubrOar base
Material.Coating head is continuously entered in tractive force effect lower network tubular substrate, while coat feed liquid is pumped into coating by metering
Head.Coating feed liquid penetrates into yarn and complete wetting cladding network tubular substrate, is applied the network tubrOar base material of feed liquid cladding
Leave continuously from coating head, the plug of rotation as scraper in the certain thickness coat of tubular substrate inner surface striking, 10%
The core liquid of DMA and 90% water mixing composition is exchanged and solidified, appearance fabric with coat progress solvent
Liquid enters coagulating bath and exchanges film forming, and 0.01 micron of the average pore size of film, internal diameter is 4mm, and external diameter is 6mm, in 0.2MPa, 25 DEG C
Under the conditions of pure water internal pressure flux be 580L/m2 .h。
Embodiment 3：
By the polyethersulfone resin of percentage by weight 17% (Belgian Su Wei companies Veradel 3000P), 62%N, N- diformazans
Base formamide, 10% polyethylene glycol 200,10% PVP K-30 and 1% sulfonated polyether sulfone are added in agitator tank,
80 DEG C are stirred 12 hours, and filtering, vacuum defoamation obtain coating feed liquid.The polyester conjugated yam of 16 deniers 1000 passes through rotation respectively
The plug turned is oriented to smooth cross winding on the external diameter 8mm hollow plug of stainless steel, and crosspoint ultra-sonic welded is bonded to network
Tubular substrate.Coating head is continuously entered in tractive force effect lower network tubular substrate, is conveyed while coating feed liquid by measuring pump
To coating head.Coating feed liquid penetrates into yarn and complete wetting cladding network tubular substrate, is applied the network pipe of feed liquid cladding
Shape base material leave continuously from coat head, the plug of rotation as scraper in the certain thickness coat of tubular substrate inner surface striking,
The core liquid of 15% DMF and 85% water mixing composition is exchanged and solidified with coat progress solvent, outside
Surface feed liquid enters coagulating bath and exchanges film forming, and 0.08 micron of the average pore size of film, internal diameter is 8mm, and external diameter is 12mm,
0.2MPa, the pure water internal pressure flux under the conditions of 25 DEG C is 2150L/m2 .h。
Embodiment 4：
By the polyethersulfone resin (BASF 6020P) of percentage by weight 18%, 70%N, dinethylformamide, 5% poly- second
Glycol 200,6% PVP K-30 and 1% sulfonated polyether sulfone are added in agitator tank, are stirred 12 hours at 80 DEG C, mistake
Filter, vacuum defoamation obtain coating feed liquid.The polyester conjugated yam of 16 deniers 900 is oriented to smooth hand over by the plug of rotation respectively
Fork is wrapped on the hollow plug of external diameter 8mm stainless steel, and crosspoint ultra-sonic welded is bonded to network tubrOar base material.In traction masterpiece
Coating head is continuously entered with lower network tubular substrate, while coat feed liquid is pumped into coating head by metering.Coating feed liquid is oozed
Enter to yarn and complete wetting cladding network tubular substrate, the network tubrOar base material for being applied feed liquid cladding leaves continuously from coating
Head, the plug of rotation as scraper in the certain thickness coat of tubular substrate inner surface striking, 30% triethyl phosphate and
The core liquid of 70% water mixing composition is exchanged and solidified with coat progress solvent, and outer surface feed liquid enters coagulating bath exchange
Film forming, is made 0.06 micron of the average pore size of the film of film, internal diameter is 4mm, and external diameter is 6mm, pure under the conditions of 0.2MPa, 25 DEG C
Water internal pressure flux is 1670L/m2 .h。
Embodiment 5：
By the polyethersulfone resin of percentage by weight 15% (Belgian Su Wei companies Veradel 3000P), 60%N, N- diformazans
Yl acetamide, 10% polyethylene glycol 200,10% PVP K-30 and 5% sulfonated polyether sulfone are added in agitator tank,
80 DEG C are stirred 12 hours, and filtering, vacuum defoamation obtain coating feed liquid.The polyester conjugated yam of 16 deniers 300 passes through rotation respectively
The plug turned is oriented to smooth cross winding on the external diameter 8mm hollow plug of stainless steel, and crosspoint ultra-sonic welded is bonded to network
Tubular substrate.Coating head is continuously entered in tractive force effect lower network tubular substrate, is conveyed while coating feed liquid by measuring pump
To coating head.Coating feed liquid penetrates into yarn and complete wetting cladding network tubular substrate, is applied the network pipe of feed liquid cladding
Shape base material leave continuously from coat head, the plug of rotation as scraper in the certain thickness coat of tubular substrate inner surface striking,
Core liquid (water) and coat carry out solvent and are exchanged and solidify, outer surface feed liquid enters coagulating bath and exchanges film forming, and film is averaged
0.03 micron of aperture, internal diameter is 8mm, and external diameter is 12mm, and the pure water internal pressure flux under the conditions of 0.2MPa, 25 DEG C is 1160L/
m2 .h。
Embodiment 6：
By the polyvinylidene fluoride resin of percentage by weight 17% (Belgian Su Wei companies Solvay Solexis 1015),
55%N- methyl pyrrolidones, 10% dimethyl sulfoxide (DMSO), 7% Macrogol 600,9% PVP K-30 and 2% are poly-
Oxygen ethene-polyoxypropylene block copolymers are added in agitator tank, are stirred 12 hours at 80 DEG C, and filtering, vacuum defoamation are coated
Feed liquid.The polyester conjugated yam of 4 deniers 200 is oriented to smooth cross winding external diameter 1.5mm's by the plug of rotation respectively
In stainless steel core bar, crosspoint ultra-sonic welded is bonded to network tubrOar base material.It is continuous in tractive force effect lower network tubular substrate
Into coating head, while coat feed liquid is pumped into coating head by metering.Coating feed liquid penetrates into yarn and complete wetting bag
Network tubrOar base material is covered, the network tubrOar base material for being applied feed liquid cladding leaves continuously from coating head, and the base material of coating feed liquid enters
Film forming is exchanged to coagulating bath, 0.05 micron of the average pore size of film, internal diameter is 1.5mm, and external diameter is 2.5mm, in 0.1MPa, 25 DEG C of bars
Pure water external pressure flux under part is 760L/m2 .h。
Embodiment 7：
By the modified poly (ether-sulfone) of percentage by weight 17%, 62%N, N- dimethyl acetamides, 10% Macrogol 600,9% gather
Vinylpyrrolidone K-30 and 2% polyox-yethylene-polyoxypropylene block copolymer are added in agitator tank, small in 80 DEG C of stirrings 12
When, filtering, vacuum defoamation obtain coating feed liquid.The polyester conjugated yam of 4 deniers 200 passes through the plug guide flat of rotation respectively
Whole cross winding is in external diameter 1.5mm stainless steel core bar, and crosspoint ultra-sonic welded is bonded to network tubrOar base material.In tractive force
Effect lower network tubular substrate continuously enters coating head, while coat feed liquid is pumped into coating head by metering.Coat feed liquid
Yarn and complete wetting cladding network tubular substrate are penetrated into, the network tubrOar base material for being applied feed liquid cladding leaves continuously from coating
Head, the base material of coating feed liquid enters coagulating bath and exchanges film forming, 0.04 micron of the average pore size of film is made, internal diameter is 1.5mm, outside
Footpath is 2.4mm, and the pure water external pressure flux under the conditions of 0.1MPa, 25 DEG C is 930L/m2 .h。
Embodiment 8：
By the polyvinylidene fluoride resin of percentage by weight 15% (Belgian Su Wei companies Solvay Solexis 6020),
50%N, dinethylformamide, 29% triethyl phosphate, 4% Macrogol 600,1% PVP K-30 and 1%
Polymethyl methacrylate is added in agitator tank, is stirred 12 hours at 80 DEG C, and filtering, vacuum defoamation obtain coating feed liquid.4 denier
The polyester conjugated yam of number 250 is oriented to stainless steel core bar of the smooth cross winding in external diameter 1.5mm by the plug of rotation respectively
On, crosspoint ultra-sonic welded is bonded to network tubrOar base material.Coating head is continuously entered in tractive force effect lower network tubular substrate,
Feed liquid is coated simultaneously, and coating head is pumped into by metering.Coating feed liquid penetrates into yarn and complete wetting cladding network tubrOar base
Material, the network tubrOar base material for being applied feed liquid cladding leaves continuously from coating head, and the base material of coating feed liquid enters coagulating bath exchange
Film forming, 0.1 micron of the average pore size of film, internal diameter is 1.5mm, and external diameter is 2.4mm, outside the pure water under the conditions of 0.1MPa, 25 DEG C
Pressure flux is 1420L/m2·h。
Claims (8)
1. a kind of preparation method of the embedded hollow composite membrane of enhancing in situ, it is characterised in that comprise the steps：
(1) it is fluoropolymer resin, pore-foaming agent, hydrophilizing agent and solvent is mixed according to 15~20: 5~20: 1~5: 55~79 weight ratio
Close, then stir, obtain coating feed liquid after filtering, vacuum defoamation；
(2) by the smooth cross winding of multi-strand yarns on the plug of rotation, the crosspoint of yarn is bonded with ultra-sonic welded, forms bag
It is rolled in the network tubrOar enhancing base materials on plug；
(3) it is continuously supplied to measuring pump by feed liquid is coated in hollow coating head, network tubrOar is strengthened base using tractive force
Material moves down along plug and continuously enters coating head；Coating feed liquid is penetrated into yarn and cladding network tubrOar completely strengthens base
While material, the plug of rotation is scraped as scraper in network tubrOar enhancing base materials inner surface makes coat；
(5) under tractive force effect, the network tubrOar enhancing base materials for being applied feed liquid cladding leave continuously from coating head into solidification
Bath, surface feed liquid and the water coke slurry film forming in coagulating bath of network tubrOar enhancing base materials, final obtained embedded enhancing in situ is hollow
Composite membrane；
Described fluoropolymer resin is polyether sulfone, modified poly (ether-sulfone), Kynoar, polysulfones, polyvinyl chloride, polyacrylonitrile or vinegar
One or two kinds of in acid cellulose；
When plug external diameter is more than 3mm, plug uses hollow tubular structure；Core liquid is introduced by its upper end, makes core liquid along core
Trickling downwards inside rod；After network tubrOar enhancing base materials complete coating in coating head, departed from by drawing from the end of plug；
Core liquid flows out from the bottom of plug, and is exchanged with the surface progress solvent of coat on the inside of network tubrOar enhancing base materials, and
Realize solidification；
The core liquid refer to one kind in water, DMA, DMF or triethyl phosphate or
Two kinds of mixed liquors；
When plug external diameter is less than 3mm, core liquid is not introduced, network tubrOar enhancing base materials are wrapped up using only coating material.
2. according to the method described in claim 1, it is characterised in that described pore-foaming agent is polyvinylpyrrolidone, polyethylene
Alcohol, polyethylene glycol, ethylene glycol, diethylene glycol (DEG) or two kinds of triethylene glycol or three kinds.
3. according to the method described in claim 1, it is characterised in that described hydrophilizing agent is sulfonated polyether sulfone, polymethyl
One kind of sour methyl esters, polyox-yethylene-polyoxypropylene block copolymer or polyether silicone.
4. according to the method described in claim 1, it is characterised in that described solvent is DMA, N, N- bis-
One or both of NMF, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), trimethyl phosphate or triethyl phosphate.
5. according to the method described in claim 1, it is characterised in that described yarn is the composite filament of denier 200~1000, its
Material is one kind in polypropylene, polyester or nylon.
6. according to the method described in claim 1, it is characterised in that described network tubrOar enhancing base materials are by 4~32 stock yarns
Line cross winding is welded, and its internal diameter is 1~12mm, and external diameter is 1.6~20mm, the mesh aperture between yarn 0.1~
2mm。
7. according to the method described in claim 1, it is characterised in that the enhancing of the obtained embedded hollow composite membrane of enhancing in situ is used
Network structure is formed in situ during composite membrane is prepared；The internal diameter of the embedded hollow composite membrane of enhancing in situ is 1
~12mm, external diameter is 1.6~20mm, and average pore size is 0.01~1 micron.
8. according to the method described in claim 1, it is characterised in that the stirring described in step (1) refers to continue at 80 DEG C
Stirring 12 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510443598.6A CN105056773B (en) | 2015-07-26 | 2015-07-26 | The preparation method of the embedded hollow composite membrane of enhancing in original position |
Applications Claiming Priority (1)
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| CN107694355A (en) * | 2017-10-16 | 2018-02-16 | 三达膜科技（厦门）有限公司 | A kind of inner support Pvdf Microporous Hollow Fiber Membrane and preparation method thereof |
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| CN103007778A (en) * | 2012-12-20 | 2013-04-03 | 北京碧水源膜科技有限公司 | Preparation method and preparation device for enhanced hollow fiber composite film |
| CN101543731B (en) * | 2009-03-23 | 2013-07-31 | 杭州洁弗膜技术有限公司 | Method for preparing fiber braided tube embedded enhanced type polymer hollow fiber microporous membrane |
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| JP2013173139A (en) * | 2013-04-09 | 2013-09-05 | Asahi Kasei Chemicals Corp | Manufacturing method of porous hollow fiber membrane |
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| CN102266726A (en) * | 2011-08-23 | 2011-12-07 | 浙江大学 | Method for preparing long fiber reinforced hollow fibrous membrane |
| CN103007778A (en) * | 2012-12-20 | 2013-04-03 | 北京碧水源膜科技有限公司 | Preparation method and preparation device for enhanced hollow fiber composite film |
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