CN105056773A - Preparation method for in-situ embedded enhanced hollow composite membrane - Google Patents
Preparation method for in-situ embedded enhanced hollow composite membrane Download PDFInfo
- Publication number
- CN105056773A CN105056773A CN201510443598.6A CN201510443598A CN105056773A CN 105056773 A CN105056773 A CN 105056773A CN 201510443598 A CN201510443598 A CN 201510443598A CN 105056773 A CN105056773 A CN 105056773A
- Authority
- CN
- China
- Prior art keywords
- base material
- network
- plug
- tubroar
- feed liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a separation membrane material preparation and enhanced modification technology, and aims to provide a preparation method for an in-situ embedded enhanced hollow composite membrane. The preparation method comprises: mixing polymer resin, a pore-foaming agent, a hydrophilc agent and a solvent to obtain a mixture, stirring the mixture, filtering the mixture, and carrying out vacuum defoamation on the mixture to obtain a coating feed liquid; flatly crossing and winding a plurality of yarns on a rotary core rod, ultrasonically welding and binding yarn crossed points to form a network tubular enhanced base material, then, downwards moving the network tubular enhanced base material along the core rod and continuously introducing the network tubular enhanced base material into a coating head; and infiltrating the coating feed liquid into the yarns and completely covering the enhanced base material, continuously leaving the coating head and entering a coagulating bath, then, enabling the feed liquid on the surface to exchange with water in the coagulating bath to form a membrane, and finally preparing the in-situ embedded enhanced hollow composite membrane. The preparation method disclosed by the invention is simple and continuous, and capable of realizing industrial production; a stripping phenomenon is avoided, so that the problem that the composite membrane is in insufficient in peel resistance strength is solved; and the in-situ embedded network tubular enhanced base material is relatively low in cost, so that the membrane material cost is finally reduced.
Description
Technical field
The invention belongs to separation membrane material preparation and strengthen technical field of modification, the present invention relates to a kind of original position and embed the preparation method strengthening hollow composite membrane.
Background technology
At present, polymer separation film has been widely applied to the fields such as sewage disposal, medicine, beverage, chemical industry, electronics, food and papermaking as the important parting material of one.Hollow-fibre membrane have specific area large, load that density is high, volume is little, treatment effeciency is high and the simple advantage of production technology, is a kind of main membrane material.In order to make cross-film resistance low, the wall thickness general thinner (about tens microns) of hollow-fibre membrane, although hollow-fibre membrane belongs to self-cradling type membrane material have certain mechanical strength, but because polymer separation film membranous wall is high voidage loose structure, still there is the shortcoming of mechanical strength deficiency when being applied to high-pressure fluid process or dither.In order to improve the mechanical strength of hollow fibre polymeric membranes, Canada Zenon company (USPatentNo.5,472,607, US2003/0098275A1, WO00/78437A1) make public for the first time a kind of technology of preparing of composite polymer hollow-fibre membrane, the polymer composite hollow fiber membrane prepared by this technology only has very thin one layer of polymeric separating layer, its thickness is 0.01 ~ 0.1mm, and the water flux of therefore obtained film increases greatly, and transmembrane pressure reduces greatly.But, polymer separation film is just compounded in the outer surface of the fiber braided tube woven in advance by this hollow-fibre membrane, therefore the binding ability between polymer separation film and fiber braided tube is bad, carrying out film, in reverse cleaning process, easily coming off between polymer separation film and fiber braided tube.Kolon Industrial Co., Ltd of Korea S (US2008/0292823A1, US2008/0305290A1, WO2008/097011A1) disclose a kind of technology by regulating the speed of travel of fiber braided tube and the ratio of casting solution extrusion capacity to control casting solution infiltration capacity.Can the infiltration capacity of casting solution be controlled within 30% by this technology, obtain composite hollow fibre microporous barrier there is the one layer of polymeric diffusion barrier that thickness is less than 0.2mm.Chinese patent CN100546702C discloses and on capillary braid, applies casting solution prepare composite membrane, coating liquid is penetrated in braid and improves compound film strength.Chinese patent CN101357303B and CN102784566B discloses first to the pre-modification coating of woven tube, then secondary coating preparation liquid prepares composite membrane.Although this similar techniques strengthens the adhesion between diffusion barrier and fiber braided tube to a certain extent, thoroughly do not solve the composite hollow fibre microporous barrier problem that polymer separation film and fiber braided tube depart from backwash process.Above-mentioned method is all generally first prepare pipe-type woven pipe, and then applies casting solution to prepare composite membrane, process gap relative complex.The braiding speed of tubular braid is comparatively slow, and the chances are prepares 1/10 of composite membrane speed, needs more braider.The thickness needing woven tube certain in order to rigidity and the circularity of tubular braid ensures, the composite membrane wall thickness that corresponding preparation all obtains increases, the external diameter that the packed density that hollow-fibre membrane is relatively high is preferably less, the internal diameter of such composite membrane is corresponding just smaller, limits the length available of the hollow-fibre membrane in encapsulating film assembly.Further, tubular braid raw material and manufacturing cost higher, improve the cost of composite membrane.
Chinese patent CN101543731B discloses a kind of preparation method of fiber braided tube embedded enhanced type polymer hollow fiber microporous membrane, it is characterized in that have employed fibrage-coextrusion integration film-forming process, be fixed in the middle of woven tube by core liquid pipe, fibre bundle is become fiber braided tube along the braiding of core liquid pipe simultaneously, again casting solution, core liquid, fiber braided tube are carried out coextrusion by extrusion die, and prepare fiber braided tube embedded enhanced type polymer hollow fiber microporous membrane by phase transition method.Fiber braided tube is successfully embedded in the body of hollow-fibre membrane by the method, and core liquid is incorporated into the inner chamber of woven tube, effectively control the internal diameter of hollow-fibre membrane, thus solve the technical barriers such as conventional application processes for forming cellulose woven tube to strengthen in hollow-fibre membrane polymeric layer and braided fiber pipe easily departs from, hollow fiber cavity easily blocks, but it is comparatively slow to there is fibrage speed in the method, limits masking efficiency and is difficult to realize industrialization.Chinese patent CN100393397C and CN101837248B discloses and first prepares hollow-fibre membrane, then outer surface is wound around fiber become net or adhering fibre silk secondary coating preparation liquid prepare composite membrane, these class methods prepare relative complex be difficult to control.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the problem that peel strength is not enough, suitability for industrialized production is difficult and membrane material cost is higher of composite membrane in prior art, provides a kind of original position to embed the preparation method strengthening hollow composite membrane.
To achieve these goals, the technical solution used in the present invention is as follows:
There is provided a kind of original position to embed the preparation method strengthening hollow composite membrane, comprise the steps:
(1) by fluoropolymer resin, pore-foaming agent, hydrophilizing agent and solvent according to the weight ratio mixing of 15 ~ 20: 5 ~ 20: 1 ~ 5: 55 ~ 79, then stir, filter, obtain after vacuum defoamation applying feed liquid;
(2) by multi-strand yarns along the smooth cross winding of gathering sill on the plug rotated, the crosspoint of yarn bonds with ultra-sonic welded, is formed to be wrapped in network tubrOar on plug and to strengthen base material;
(3) with measuring pump, coating feed liquid is continued to be transported in the application head of hollow, utilize tractive force to make network tubrOar strengthen base material and move down along plug and enter application head continuously; Coating feed liquid penetrates in yarn and while complete coated network tubrOar strengthens base material, and the plug of rotation strengthens base material inner surface as scraper at network tubrOar and scrapes and make coat;
(5) under tractive force effect, the coated network tubrOar of coated feed liquid strengthens base material and leaves application head continuously and enter coagulating bath, network tubrOar strengthens the water coke slurry film forming in surperficial feed liquid and the coagulating bath of base material, and final obtained original position embeds enhancing hollow composite membrane.
In the present invention, described fluoropolymer resin is one in polyether sulfone, modified poly (ether-sulfone), Kynoar, polysulfones, polyvinyl chloride, polyacrylonitrile or cellulose acetate or two kinds.
In the present invention, described pore-foaming agent is two kinds or three kinds of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, ethylene glycol, diethylene glycol (DEG) or triethylene glycol.
In the present invention, described hydrophilizing agent is the one of sulfonated polyether sulfone, polymethyl methacrylate, polyox-yethylene-polyoxypropylene block copolymer or polyether silicone.
In the present invention, described solvent is one or both in DMA, DMF, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), trimethyl phosphate or triethyl phosphate.
In the present invention, described yarn is the composite filament of dawn number 200 ~ 1000, and its material is the one in polypropylene, polyester or nylon.
In the present invention, it is be wound around by 4 ~ 32 bursts of yarn crossovers to be welded that described network tubrOar strengthens base material, and its internal diameter is 1 ~ 12mm, and external diameter is 1.6 ~ 20mm, and the mesh aperture between yarn is at 0.1 ~ 2mm.
In the present invention, when plug external diameter is greater than 3mm, plug adopts the tubular structure of hollow; Introduce core liquid by its upper end, make core liquid along the inner trickling downwards of plug; Network tubrOar strengthens after base material completes coating in application head, is pulled to depart from from the end of plug; Core liquid flows out from the bottom of plug, and carries out solvent with the surface that network tubrOar strengthens coat inside base material and exchange mutually, and realizes solidification;
Described core liquid refers to one in water, DMA, DMF or triethyl phosphate or two kinds of mixed liquors;
When plug external diameter is less than 3mm, do not introduce core liquid, only use coating material parcel network tubrOar to strengthen base material.
In the present invention, it is formed at the process situ preparing composite membrane that obtained original position embeds the enhancing network structure strengthening hollow composite membrane; It is 1 ~ 12mm that described original position embeds the internal diameter strengthening hollow composite membrane, and external diameter is 1.6 ~ 20mm, and average pore size is 0.01 ~ 1 micron.
In the present invention, the stirring described in step (1) to refer at 80 DEG C Keep agitation 12 hours.
The original position utilizing the method for the invention obtained embeds and strengthens hollow composite membrane product, and if composite membrane internal diameter is at 1-2mm, external diameter is hollow-fibre membrane at 1.6-3mm, and predominant package is that external-compression type component application is in immersion MBR (film biological reactor); If internal diameter is at 2-12mm, external diameter is tubular membrane at 3-20mm, and predominant package is that inner pressed is applied to percolate, process containing the high-solids content liquid material such as sewage, fruit juice of activated sludge.When plug external diameter is greater than 3mm, hollow rigid pipe can be adopted; When plug external diameter is less than 3mm, solid, rigid rod can be adopted, now just not need to adopt the technique of adding core liquid.
Compared with prior art, beneficial effect of the present invention is:
(1) preparation method is simple, continuous, and can realize suitability for industrialized production;
(2) there is not peeling in the present invention, overcomes the problem of the peel strength deficiency of composite membrane in prior art;
(3) it is lower that the network tubrOar that original position embeds strengthens base material cost, final reduction membrane material cost.
Accompanying drawing explanation
Fig. 1 is that original position embeds enhancing hollow composite membrane preparation technology schematic flow sheet.
Fig. 2 is that original position embeds enhancing hollow composite membrane Preparation equipment schematic diagram.
In figure: coating feed liquid dissolving tank 1, coating material metering and conveying device 2, coating feed liquid 21, yarn actinobacillus device 3, yarn 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, Mandrel Rotating device 7, rotary system 71, Mandrel Rotating connector 72, swivel joint 8, ultrasonic welding device 9, ultrasonic generator 91, ultrasonic bond joint 92, plug fixture 10, application head 11, gel water bath 12, spiral filament forming machine 13, strengthen hollow composite membrane 14.
Detailed description of the invention
Below in conjunction with accompanying drawing, embodiments of the present invention are described in detail.
First need statement, the preparation original position introduced below embeds the device strengthening hollow composite membrane, is only the content of the present invention for example, can not be considered as the present invention and can only rely on the realization of this equipment.Therefore, the explanation of relevant devices should not be considered to be and limit technology of the present invention.Those skilled in the art are after understanding implementation method of the present invention, and the technical ability all grasped by it carries out design or the manufacture of equipment.
In the present embodiment, preparation original position embeds the device strengthening hollow composite membrane and comprises gel water bath 12 and spiral filament forming machine 13, and application system, yarn actinobacillus device and feed liquid induction system; Wherein,
Application system comprises plug 6, ultrasonic welding device 9, plug fixture 10 and application head 11.
Plug 6 is stainless steel hollow tube or solid tubes, and external diameter is 1.5 ~ 12mm, is preferably greater than 3mm hollow tube.Plug 6 upper end outer surface is uniformly distributed screw-shaped groove as yarn guide groove, and it arranges object is multi-strand yarns along the smooth cross winding of gathering sill on the plug rotated.
Plug 6 is vertically suspended from the top of gel water bath 12, and the upper end of plug 6 realizes being connected with core liquid pipe 51 by Mandrel Rotating connector 72, swivel joint 8, and Mandrel Rotating connector 72 connects with rotary system 71.
Plug 6 is downwards successively through ultrasonic welding device 9, plug fixture 10 and application head 11; Ultrasonic welding device 9 comprises ultrasonic generator 91 and ultrasonic bond joint 92.Keep spacing between plug fixture 10 and plug 6, enable plug 6 realize rotating around the axle center of self while being fixed.Application head 11 is hollow structure, and its inner space is connected with the output pipe of coating material metering and conveying device 1; Described plug 6 is from top to bottom through the inner space of application head 11.
Yarn actinobacillus device comprises yarn ureeling barrel 31 and yarn unwrapping wire rotary system 32, and the quantity of yarn actinobacillus device can be 1 ~ 8 group.Often organize yarn actinobacillus device and have 2 yarn ureeling barrels 31 at least, and be divided into the both sides on plug 6 top;
Feed liquid induction system comprises coating feed liquid dissolving tank 1 and core flow container 4, is connected to application head 11, is connected to core liquid pipe 51 at the bottom of the tank of core flow container 4 by pipeline and core liquid metering and conveying device 5 at the bottom of the tank of coating feed liquid dissolving tank 1 by pipeline and coating material metering and conveying device 2.Coating material metering and conveying device 2 and core liquid metering and conveying device 5 all can adopt measuring pump.
Of the present inventionly realize principle:
Core liquid trickles downwards along the empty internal of plug 6 through swivel joint 8, Mandrel Rotating connector 72 after delivering to core liquid pipe 51 by core liquid metering and conveying device 5.Rotary system 71 drives Mandrel Rotating connector 72, makes plug 6 rotate (core liquid pipe 51 and swivel joint 8 maintain static) around the axis of himself.The mandrel outer surface that the smooth cross winding of yarn on multiple yarn ureeling barrel 31 is rotating, bonding is welded by ultrasonic welding device 9 in its crosspoint, thus forms network tubrOar enhancing base material.The network tubrOar having completed welding before this strengthens base material under the traction of spiral filament forming machine 13, constantly descending and finally departed from by bottom after applying feed liquid along plug 6.Coating feed liquid is transported to application head 11 by coating material metering and conveying device 2 and fills up its cavity, when network tubrOar strengthens base material when continuing to pass through application head 11. coating feed liquid penetrates into yarn and the coated network tubrOar of complete wetting strengthens base material.The plug 6 rotated is as scraper, and the inner surface striking strengthening base material at network tubrOar forms certain thickness coat.Then, core liquid carries out solvent with the inner surface of coat in the bottom of plug 6 and exchanges mutually and solidify, and outermost feed liquid continues to be exchanged into film entering into gel water bath 12.
In the present invention, when plug 6 external diameter is greater than 3mm, plug 6 adopts the tubular structure of hollow; Introduce the liquid-solid metallization processes of core; When plug 6 external diameter is less than 3mm, do not introduce core liquid, only use coating material parcel network tubrOar to strengthen base material.
Embodiment 1:
By weight percentage by 20% polyethersulfone resin (BASF 6020P), 55%N, dinethylformamide, 11% Macrogol 200,9% PVP K-30 and 5% sulfonated polyether sulfone add in agitator tank, stir 12 hours at 80 DEG C, filtration, vacuum defoamation obtain applying feed liquid.The polyester conjugated yam of 8 dawn numbers 750 leads smooth cross winding on the stainless steel hollow plug of external diameter 4mm respectively by the plug rotated, and crosspoint ultra-sonic welded is bonded to network tubrOar base material.Enter application head continuously in tractive force effect lower network tubular substrate, apply feed liquid simultaneously and be transported to application head by measuring pump.Coating feed liquid penetrates into yarn and the coated network tubular substrate of complete wetting, the coated network tubrOar base material of coated feed liquid leaves application head continuously, rotate plug as scraper at the certain thickness coat of tubular substrate inner surface striking, core liquid (water) and coat carry out solvent and exchange mutually and solidify, outer surface feed liquid enters into coagulating bath and exchanges film forming, the average pore size of film 0.02 micron, internal diameter is 4mm, external diameter is 6mm, at 0.2MPa, in the pure water under 25 DEG C of conditions, pressure flux is 740L/m
2 .h.
Embodiment 2:
20% polyethersulfone resin (BASF 6020P), 50%N by weight percentage, N-dimethylacetylamide, 20% trimethyl phosphate, 6% Macrogol 200,3% PVP K-30 and 1% sulfonated polyether sulfone add in agitator tank, stir 12 hours at 80 DEG C, filtration, vacuum defoamation obtain applying feed liquid.The polyester conjugated yam of 8 dawn numbers 750 leads smooth cross winding on the stainless steel hollow plug of external diameter 4mm respectively by the plug rotated, and crosspoint ultra-sonic welded is bonded to network tubrOar base material.Enter application head continuously in tractive force effect lower network tubular substrate, apply feed liquid simultaneously and be transported to application head by measuring pump.Coating feed liquid penetrates into yarn and the coated network tubular substrate of complete wetting, the coated network tubrOar base material of coated feed liquid leaves application head continuously, rotate plug as scraper at the certain thickness coat of tubular substrate inner surface striking, the N of 10%, N-dimethylacetylamide carries out solvent with the core liquid of the water mixing composition of 90% with coat and exchanges mutually and solidify, outer surface feed liquid enters into coagulating bath and exchanges film forming, the average pore size of film 0.01 micron, internal diameter is 4mm, external diameter is 6mm, at 0.2MPa, in the pure water under 25 DEG C of conditions, pressure flux is 580L/m
2 .h.
Embodiment 3:
By percentage by weight 17% polyethersulfone resin (Belgian Su Wei company Veradel3000P), 62%N, dinethylformamide, 10% Macrogol 200,10% PVP K-30 and 1% sulfonated polyether sulfone add in agitator tank, stir 12 hours at 80 DEG C, filtration, vacuum defoamation obtain applying feed liquid.The polyester conjugated yam of 16 dawn numbers 1000 leads smooth cross winding on the stainless steel hollow plug of external diameter 8mm respectively by the plug rotated, and crosspoint ultra-sonic welded is bonded to network tubrOar base material.Enter application head continuously in tractive force effect lower network tubular substrate, apply feed liquid simultaneously and be transported to application head by measuring pump.Coating feed liquid penetrates into yarn and the coated network tubular substrate of complete wetting, the coated network tubrOar base material of coated feed liquid leaves application head continuously, rotate plug as scraper at the certain thickness coat of tubular substrate inner surface striking, the N of 15%, dinethylformamide carries out solvent with the core liquid of the water mixing composition of 85% with coat and exchanges mutually and solidify, outer surface feed liquid enters into coagulating bath and exchanges film forming, the average pore size of film 0.08 micron, internal diameter is 8mm, external diameter is 12mm, at 0.2MPa, in the pure water under 25 DEG C of conditions, pressure flux is 2150L/m
2 .h.
Embodiment 4:
By percentage by weight 18% polyethersulfone resin (BASF 6020P), 70%N, dinethylformamide, 5% Macrogol 200,6% PVP K-30 and 1% sulfonated polyether sulfone add in agitator tank, stir 12 hours at 80 DEG C, filtration, vacuum defoamation obtain applying feed liquid.The polyester conjugated yam of 16 dawn numbers 900 leads smooth cross winding on the stainless steel hollow plug of external diameter 8mm respectively by the plug rotated, and crosspoint ultra-sonic welded is bonded to network tubrOar base material.Enter application head continuously in tractive force effect lower network tubular substrate, apply feed liquid simultaneously and be transported to application head by measuring pump.Coating feed liquid penetrates into yarn and the coated network tubular substrate of complete wetting, the coated network tubrOar base material of coated feed liquid leaves application head continuously, rotate plug as scraper at the certain thickness coat of tubular substrate inner surface striking, the triethyl phosphate of 30% carries out solvent with the core liquid of the water mixing composition of 70% with coat and exchanges mutually and solidify, outer surface feed liquid enters into coagulating bath and exchanges film forming, the average pore size 0.06 micron of the film of obtained film, internal diameter is 4mm, external diameter is 6mm, at 0.2MPa, in the pure water under 25 DEG C of conditions, pressure flux is 1670L/m
2 .h.
Embodiment 5:
By percentage by weight 15% polyethersulfone resin (Belgian Su Wei company Veradel3000P), 60%N, N-dimethylacetylamide, 10% Macrogol 200,10% PVP K-30 and 5% sulfonated polyether sulfone add in agitator tank, stir 12 hours at 80 DEG C, filtration, vacuum defoamation obtain applying feed liquid.The polyester conjugated yam of 16 dawn numbers 300 leads smooth cross winding on the stainless steel hollow plug of external diameter 8mm respectively by the plug rotated, and crosspoint ultra-sonic welded is bonded to network tubrOar base material.Enter application head continuously in tractive force effect lower network tubular substrate, apply feed liquid simultaneously and be transported to application head by measuring pump.Coating feed liquid penetrates into yarn and the coated network tubular substrate of complete wetting, the coated network tubrOar base material of coated feed liquid leaves application head continuously, rotate plug as scraper at the certain thickness coat of tubular substrate inner surface striking, core liquid (water) and coat carry out solvent and exchange mutually and solidify, outer surface feed liquid enters into coagulating bath and exchanges film forming, the average pore size of film 0.03 micron, internal diameter is 8mm, external diameter is 12mm, at 0.2MPa, in the pure water under 25 DEG C of conditions, pressure flux is 1160L/m
2 .h.
Embodiment 6:
Percentage by weight 17% polyvinylidene fluoride resin (Belgian Su Wei company SolvaySolexis1015), 55%N-methyl pyrrolidone, 10% dimethyl sulfoxide (DMSO), 7% Macrogol 600,9% PVP K-30 and 2% polyox-yethylene-polyoxypropylene block copolymer are added in agitator tank, stir 12 hours at 80 DEG C, filtration, vacuum defoamation obtain applying feed liquid.The polyester conjugated yam of 4 dawn numbers 200 leads smooth cross winding on the stainless steel plug of external diameter 1.5mm respectively by the plug rotated, and crosspoint ultra-sonic welded is bonded to network tubrOar base material.Enter application head continuously in tractive force effect lower network tubular substrate, apply feed liquid simultaneously and be transported to application head by measuring pump.Coating feed liquid penetrates into yarn and the coated network tubular substrate of complete wetting, the coated network tubrOar base material of coated feed liquid leaves application head continuously, the base material of coating feed liquid enters into coagulating bath and exchanges film forming, the average pore size of film 0.05 micron, internal diameter is 1.5mm, external diameter is 2.5mm, and at 0.1MPa, the pure water external pressure flux under 25 DEG C of conditions is 760L/m
2 .h.
Embodiment 7:
By percentage by weight 17% modified poly (ether-sulfone), 62%N, N-dimethylacetylamide, 10% Macrogol 600,9% PVP K-30 and 2% polyox-yethylene-polyoxypropylene block copolymer add in agitator tank, stir 12 hours at 80 DEG C, filtration, vacuum defoamation obtain applying feed liquid.The polyester conjugated yam of 4 dawn numbers 200 leads smooth cross winding on the stainless steel plug of external diameter 1.5mm respectively by the plug rotated, and crosspoint ultra-sonic welded is bonded to network tubrOar base material.Enter application head continuously in tractive force effect lower network tubular substrate, apply feed liquid simultaneously and be transported to application head by measuring pump.Coating feed liquid penetrates into yarn and the coated network tubular substrate of complete wetting, the coated network tubrOar base material of coated feed liquid leaves application head continuously, the base material of coating feed liquid enters into coagulating bath and exchanges film forming, the average pore size 0.04 micron of obtained film, internal diameter is 1.5mm, external diameter is 2.4mm, and at 0.1MPa, the pure water external pressure flux under 25 DEG C of conditions is 930L/m
2 .h.
Embodiment 8:
By percentage by weight 15% polyvinylidene fluoride resin (Belgian Su Wei company SolvaySolexis6020), 50%N, dinethylformamide, 29% triethyl phosphate, 4% Macrogol 600,1% PVP K-30 and 1% polymethyl methacrylate add in agitator tank, stir 12 hours at 80 DEG C, filtration, vacuum defoamation obtain applying feed liquid.The polyester conjugated yam of 4 dawn numbers 250 leads smooth cross winding on the stainless steel plug of external diameter 1.5mm respectively by the plug rotated, and crosspoint ultra-sonic welded is bonded to network tubrOar base material.Enter application head continuously in tractive force effect lower network tubular substrate, apply feed liquid simultaneously and be transported to application head by measuring pump.Coating feed liquid penetrates into yarn and the coated network tubular substrate of complete wetting, the coated network tubrOar base material of coated feed liquid leaves application head continuously, the base material of coating feed liquid enters into coagulating bath and exchanges film forming, the average pore size of film 0.1 micron, internal diameter is 1.5mm, external diameter is 2.4mm, and at 0.1MPa, the pure water external pressure flux under 25 DEG C of conditions is 1420L/m
2h.
Claims (10)
1. original position embeds the preparation method strengthening hollow composite membrane, it is characterized in that, comprises the steps:
(1) by fluoropolymer resin, pore-foaming agent, hydrophilizing agent and solvent according to the weight ratio mixing of 15 ~ 20: 5 ~ 20: 1 ~ 5: 55 ~ 79, then stir, filter, obtain after vacuum defoamation applying feed liquid;
(2) by smooth for multi-strand yarns cross winding on the plug rotated, the crosspoint of yarn bonds with ultra-sonic welded, is formed to be wrapped in network tubrOar on plug and to strengthen base material;
(3) with measuring pump, coating feed liquid is continued to be transported in the application head of hollow, utilize tractive force to make network tubrOar strengthen base material and move down along plug and enter application head continuously; Coating feed liquid penetrates in yarn and while complete coated network tubrOar strengthens base material, and the plug of rotation strengthens base material inner surface as scraper at network tubrOar and scrapes and make coat;
(5) under tractive force effect, the coated network tubrOar of coated feed liquid strengthens base material and leaves application head continuously and enter coagulating bath, network tubrOar strengthens the water coke slurry film forming in surperficial feed liquid and the coagulating bath of base material, and final obtained original position embeds enhancing hollow composite membrane.
2. method according to claim 1, is characterized in that, described fluoropolymer resin is one in polyether sulfone, modified poly (ether-sulfone), Kynoar, polysulfones, polyvinyl chloride, polyacrylonitrile or cellulose acetate or two kinds.
3. method according to claim 1, is characterized in that, described pore-foaming agent is two kinds or three kinds of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, ethylene glycol, diethylene glycol (DEG) or triethylene glycol.
4. method according to claim 1, is characterized in that, described hydrophilizing agent is the one of sulfonated polyether sulfone, polymethyl methacrylate, polyox-yethylene-polyoxypropylene block copolymer or polyether silicone.
5. method according to claim 1, is characterized in that, described solvent is one or both in DMA, DMF, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), trimethyl phosphate or triethyl phosphate.
6. method according to claim 1, is characterized in that, described yarn is the composite filament of dawn number 200 ~ 1000, and its material is the one in polypropylene, polyester or nylon.
7. method according to claim 1, is characterized in that, it is be wound around by 4 ~ 32 bursts of yarn crossovers to be welded that described network tubrOar strengthens base material, and its internal diameter is 1 ~ 12mm, and external diameter is 1.6 ~ 20mm, and the mesh aperture between yarn is at 0.1 ~ 2mm.
8., according to the method described in claim 1 to 7 any one, it is characterized in that,
When plug external diameter is greater than 3mm, plug adopts the tubular structure of hollow; Introduce core liquid by its upper end, make core liquid along the inner trickling downwards of plug; Network tubrOar strengthens after base material completes coating in application head, is pulled to depart from from the end of plug; Core liquid flows out from the bottom of plug, and carries out solvent with the surface that network tubrOar strengthens coat inside base material and exchange mutually, and realizes solidification;
Described core liquid refers to one in water, DMA, DMF or triethyl phosphate or two kinds of mixed liquors;
When plug external diameter is less than 3mm, do not introduce core liquid, only use coating material parcel network tubrOar to strengthen base material.
9. method according to claim 8, is characterized in that, it is formed at the process situ preparing composite membrane that obtained original position embeds the enhancing network structure strengthening hollow composite membrane; It is 1 ~ 12mm that described original position embeds the internal diameter strengthening hollow composite membrane, and external diameter is 1.6 ~ 20mm, and average pore size is 0.01 ~ 1 micron.
10. method according to claim 8, is characterized in that, the stirring described in step (1) to refer at 80 DEG C Keep agitation 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)
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105056773A true CN105056773A (en) | 2015-11-18 |
| CN105056773B CN105056773B (en) | 2017-08-15 |
Family
ID=54486412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510443598.6A Active CN105056773B (en) | 2015-07-26 | 2015-07-26 | The preparation method of the embedded hollow composite membrane of enhancing in original position |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105056773B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106215712A (en) * | 2016-07-28 | 2016-12-14 | 北京清源创智科技有限公司 | The shaped device of hollow fiber composite membrane |
| 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 |
| CN110075719A (en) * | 2019-05-30 | 2019-08-02 | 北京化工大学 | The preparation method of high-throughput polyacrylonitrile hollow fiber composite gas separation membrane |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| JP2013173139A (en) * | 2013-04-09 | 2013-09-05 | Asahi Kasei Chemicals Corp | Manufacturing method of porous hollow fiber membrane |
| US20150136691A1 (en) * | 2011-12-13 | 2015-05-21 | MEMSTAR (Guangzhou) Co. Ltd | Method for preparing double layered porous hollow membrane and device and product thereof |
-
2015
- 2015-07-26 CN CN201510443598.6A patent/CN105056773B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102266726A (en) * | 2011-08-23 | 2011-12-07 | 浙江大学 | Method for preparing long fiber reinforced hollow fibrous membrane |
| US20150136691A1 (en) * | 2011-12-13 | 2015-05-21 | MEMSTAR (Guangzhou) Co. Ltd | Method for preparing double layered porous hollow membrane and device and product thereof |
| 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 |
| JP2013173139A (en) * | 2013-04-09 | 2013-09-05 | Asahi Kasei Chemicals Corp | Manufacturing method of porous hollow fiber membrane |
Non-Patent Citations (1)
| Title |
|---|
| 胡忠举等: "《现代制造工程技术实践》", 31 January 2014, 北京：机械工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106215712A (en) * | 2016-07-28 | 2016-12-14 | 北京清源创智科技有限公司 | The shaped device of hollow fiber composite membrane |
| 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 |
| CN110075719A (en) * | 2019-05-30 | 2019-08-02 | 北京化工大学 | The preparation method of high-throughput polyacrylonitrile hollow fiber composite gas separation membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105056773B (en) | 2017-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101543731B (en) | Method for preparing fiber braided tube embedded enhanced type polymer hollow fiber microporous membrane | |
| CN101837248B (en) | Production method of cellosilk enhanced compound hollow fiber membrane | |
| CN102665878B (en) | Non-braided, textile-reinforced hollow fiber membrane | |
| CN101068613B (en) | Reinforced capillary membranes and process for manufacturing thereof | |
| US7081273B2 (en) | Method for producing defect free composite membranes | |
| EP1687133B1 (en) | Composite porous materials and methods of making and using the same | |
| CN103432916A (en) | Preparation method of enhanced hollow polyvinylidene fluoride fiber membrane | |
| CN105056773A (en) | Preparation method for in-situ embedded enhanced hollow composite membrane | |
| KR101009403B1 (en) | Process for production of hollow-fiber membrane bundles | |
| CN105727759A (en) | High-performance forward permeable membrane and electrostatic spinning preparation method thereof | |
| CN103501881A (en) | Hollow fiber membrane having a reinforced monofilament | |
| WO2008097011A1 (en) | A tubular braid and composite hollow fiber membrane using the same | |
| JP2009536573A (en) | Porous composite membrane material and its application | |
| CN102160967A (en) | Lining-reinforced hollow fiber membrane tube as well as preparation device and preparation method thereof | |
| CN104815563A (en) | Reinforced hollow fibrous membrane and preparation method thereof | |
| CN101254420A (en) | Reinforced tubular porous body compound film, method of preparing the same and use thereof | |
| CN110327787A (en) | A kind of enhancement type hollow fiber film, preparation method and device | |
| CN202410531U (en) | Outer support enhancement type hollow fiber membrane | |
| CN106861462A (en) | A kind of composite braided pipe strengthens the preparation method of PVDF hollow-fibre membranes | |
| CN102824859A (en) | Method for preparing hollow fiber nanofiltration membrane by using thermally induced phase separation/interface cross linking synchronization method | |
| HU231006B1 (en) | Composite hollow fiber membrane and method for manufacturing same | |
| KR101514665B1 (en) | Multi-layer Hollow Fiber Membrane Having High Strength and Excellent Permeability and Preparing Method Thereof | |
| CN101804305B (en) | Conductive reinforced tubular porous body composite film, preparation method thereof, and use thereof in waste water dephosphorization | |
| JP2005296937A (en) | Hollow fiber membrane module and production method therefor | |
| JP6618708B2 (en) | Method for operating hollow fiber membrane module and filtration device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |