CN101766960A - Composite hollow fiber membrane and preparation method thereof - Google Patents
Composite hollow fiber membrane and preparation method thereof Download PDFInfo
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- CN101766960A CN101766960A CN200810246644A CN200810246644A CN101766960A CN 101766960 A CN101766960 A CN 101766960A CN 200810246644 A CN200810246644 A CN 200810246644A CN 200810246644 A CN200810246644 A CN 200810246644A CN 101766960 A CN101766960 A CN 101766960A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1212—Coextruded layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/003—Organic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
Abstract
The invention relates to a composite hollow fiber membrane, single fiber of the composite hollow fiber membrane consists of a hole-forming component and a support component, wherein the support component is continuously distributed along the axial direction of each fiber in the composite hollow fiber membrane. The hole-forming component and the support component are one or any combination of a plurality of types of thermoplastic resin material, which are polyphenylene sulfide preferentially. The content by weight of the support component accounts for 2-90% of the total weight of the fiber membrane, which is 5%-8% preferentially, and 10-80% more preferentially. The preparation method of the composite hollow fiber membrane comprises the following steps: blending the hole-forming component with a hole-forming agent, carrying out granulation, then respectively extruding with the support component, and carrying out composition; carrying out drawing and heat setting treatment on obtained composite fibers obtained by composition; soaking the composite fibers after drawing and heat setting in a solvent for removing the hole-forming agent; and carrying out aerobic thermal cross-linking treatment on the composite fibers after removing the hole-forming agent, and obtaining the composite hollow fiber membrane. The composite hollow fiber membrane has the advantages of high temperature resistance, acid-alkali resistance and a wide range of applications.
Description
Technical field
The present invention relates to a kind of tunica fibrosa and preparation method thereof, relate to a kind of composite hollow fiber membrane and preparation method thereof in particular.
Background technology
In recent years, the filter method that adopts porous hollow fiber membrane is popularized obtaining aspect the filtration widely with its special advantages.At present thimble tube spinneret spinnings that adopt solwution method by a kind of annular hollow, the method for using stretching pore-forming or thermic to be separated then is prepared more.
For example patent application 200680037850.2 promptly discloses a kind of like this hollow-fibre membrane of preparation, it is for using the doughnut moulding nozzle of the plural circular extrusion that is configured to concentric circles, carrying out multilayered molten by this circular extrusion extrudes, the melting mixing thing that to form different mutually thermoplastic resins and organic liquid respectively is circular from mutual adjacent circular extrusion and extrudes, be shaped to hollow fiber through cooling curing, from this cooling curing hollow fiber thing, extract then and remove organic liquid, thereby make porous multilayered hollow-fibre membrane.The tunica fibrosa porous that this method is made, and be evenly distributed, filter efficiency and effect can be improved.But this tunica fibrosa is owing to have hole, thereby greatly reduces fibre strength, limits its application in more areas.
In order to improve this doughnut film strength, patent application 200610015575.6 discloses a kind of fibre structure that has riffled tube.It is specially extrudes the compound bunchy in back with 2～8 fibers by solwution method, forms a pencil hollow-fibre membrane, in the middle of the while continuous muscle wire material is set and strengthens.Described muscle wire material can be organic polymer fibers such as cotton rope, nylon, polyimides, aromatic polyamides, polypropylene, polyethylene etc.Yet, when filter pressure big, when filtering the environment difference, this several fibers and muscle line obvolvent structure together often are difficult to keep, its use field still is restricted.
In view of this, special proposition the present invention, composite hollow fiber membrane intensity height of the present invention, the scope of application is wide.
Summary of the invention
One of the object of the invention is to provide a kind of composite hollow fiber membrane, described tunica fibrosa intensity height, and the scope of application is wide;
Another purpose of the present invention is to provide the preparation method of described composite hollow fiber membrane, and described preparation method is simple.
In order to realize the foregoing invention purpose, the spy takes following technical scheme:
A kind of composite hollow fiber membrane, described composite hollow fiber membrane single fiber are by hole-forming component and support component and constitute, and described support component is continuous in the fiber axial directional distribution in composite hollow fiber membrane, is preferably described support component with the parallel distribution of fiber.
The axial direction of described fiber is the direction that can stretch after fiber is extruded from spinneret orifice, just the direction of the length of saying usually.Described support group branch is coated in the fiber, this support group is divided into continuous integral body, and its cross sectional shape can be the Any shape that can realize, such as triangle, quadrangle, polygon, circle or ellipse, above-mentioned shape can be rule in addition for irregular, wherein be preferably circle.
The extension of the support component of fiber can be extended for being regular or irregular curve or broken line, but is preferably linearly extension, also can more preferably distribute with the parallel extension of fiber itself.
Described support component area ratio on the composite fibre cross section can be arbitrary value, and promptly every support component can be very thick, even its edge can reach fiber inward flange and outward flange; Every support component also can be very thin, but the supporting role meeting decreases.In order further to improve the intensity of fiber, the ratio that the preferred described support component gross area accounts for the fibre section area can be: 2%～90%, more preferably 5～70%, most preferably be 10%～30%.
Hollow-fibre membrane of the present invention can adopt and be equipped with as shown in Figure 2 that the spray silk equipment of shower nozzle is prepared, this equipment is the spray silk equipment of existing hollow-fibre membrane, wherein 21 are the ring-type injector hollow space for the fused fiber ejection, a little tiny pipelines 22 evenly are set then, these pipelines are used to inject the support component of fusion, the support group dosis refracta that described pipeline quantity is provided with as required and deciding Figure 2 shows that 3 described pipelines.Described pipeline extend in the ring-type hollow space 21 of shower nozzle, the pipeline length that extend into ring-type hollow space 21 can be determined according to the needs that the position of supporting component is set, preferably the opening of pipeline 22 inserting ends is arranged on the middle place of annular hollow part 21, promptly makes support group divide inside and outside two inwalls distance to equate apart from doughnut.
When the hole-forming component fibrous material of fusion was extruded from ring-type hollow space 21, the support component of fusion was also injected ring-type hollow space 21 from pipeline 22, and moves to the spout place under the promotion of hole-forming component, thereby forms continuous supporting construction.This supporting construction is embedded in the hole-forming component.
Compound doughnut structure of the present invention has overcome patent application 200610015575.6 described plurality of fibers and the compound structure resolvent defective when the filtration environment is relatively poor of a muscle line.It all can keep structural integrity under any extreme filtercondition, can be applied to the filtration under the various situations.
According to foregoing composite hollow fiber membrane, described composite hollow fiber membrane surface apertures is 0.01～20 μ m, and surperficial percent opening is 10～90%, and film external diameter 8～1000 μ m, film internal diameter are 3～900 μ m; Being preferably surface apertures is 0.1～10 μ m, and surperficial percent opening is 20～80%; Film external diameter 10～900 μ m, film internal diameter are 5～800 μ m; More preferably surface apertures is 0.2～0.3 μ m, and surperficial percent opening is 25～40%; Film external diameter 20～350 μ m, film internal diameter are 10～300 μ m.
According to foregoing composite hollow fiber membrane, described hole-forming component can be one or more any combinations in the thermoplastic resin material, described thermoplastic resin is the notion that those skilled in the art knew usually, this area has the common definition of described thermoplastic resin, for example can be referring to this thermoplastic resin of enumerating in the patent application 200680037850.2, for example can be polyester more specifically, polyether-ether-ketone, polyethylene, polyolefin such as polypropylene, polyvinylidene fluoride, polyamide, PEI, polystyrene, polysulfones, polyvinyl alcohol, polyphenylene oxide, polyphenylene sulfide etc.Yet polyphenylene sulfide more preferably also.
This hollow-fibre membrane that uses polyphenylene sulfide to make has better working strength, and it is more acidproof, alkaline-resisting and high temperature resistant, and this tunica fibrosa can be used for various extreme filtration environment, and it is aging to be difficult for decomposition, has more durable service life.Can remedy the existing inaccessiable filtration art of tunica fibrosa.
According to foregoing composite hollow fiber membrane, described support group is divided into one or more any combinations in the thermoplastic resin material, wherein is preferably polyphenylene sulfide.
Yet can also preferred described hole-forming component with described support group be divided into one or more identical thermoplastic resin materials arbitrarily combination make, especially be preferably described hole-forming component and be divided into identical a kind of thermoplastic resin material with support group and make.When described hole-forming component is identical with the component that supports component, the two mutually combines even more ideal, when especially the two is identical one-component, intermolecular uniformity has caused hole-forming component and has supported combining closely of component, the compound interface inconsistent problem that do not exist of two components, the interface is in conjunction with better, and fabric integer intensity strengthens greatly like this, thereby under extreme conditions also can not scatter.
According to foregoing composite hollow fiber membrane, can further preferred described hole-forming component be polyphenylene sulfide with the support component.
When described hole-forming component was polyphenylene sulfide with the support component, the fibre machinery intensity of described composite hollow fiber membrane can be born 80～120kPa pressure, keeps the grown form more than 5～20 minutes.Acid and alkali-resistance: soak 5～12 days intensity forms in the various acid-base solutions and remain unchanged; High temperature resistant: as can be 130 ℃～230 ℃ long-term down in temperature and to use.Fire resistance: limited oxygen index is 30～40%; Corrosion-resistant: as to be insoluble under 200 ℃ and to appoint the river solvent.
According to foregoing composite hollow fiber membrane, described composite hollow fiber membrane by support component and hole-forming component respectively after the fusion compound extruding form.
According to foregoing composite hollow fiber membrane, described support component weight content is 2～90% of a tunica fibrosa gross weight, is preferably 5.2～88.6%, more preferably 10～80%.
The preparation method of composite hollow fiber membrane noted earlier, comprising following steps:
A, with hole-forming component and pore former blend granulation, then with support component compound extruding after the fusion respectively, obtain compound doughnut;
B, the compound compound doughnut that obtains stretched and thermal finalization is handled;
C, the compound doughnut after the stretching thermal finalization is removed pore former in solvent, obtain composite hollow fiber membrane.
According to foregoing preparation method, wherein:
Step a is described to be extruded to adopting screw extruder to extrude, described extruding under 100～350 ℃, extruding, described compound be down compound at 110～350 ℃, be preferably under 290～345 ℃ and extrude, compound down at 295～350 ℃, more preferably under 300～330 ℃, extrude, compound down at 305～330 ℃; Described pore former comprises organic pore former and inorganic pore former; That described organic pore former is preferably is polyamide-based, TPO or polyesters, described polyamide-based nylon 6 or the nylon 66 of being preferably, described TPO is preferably polyethylene, polyvinyl chloride, polystyrene or polypropylene, and described polyesters is preferably PETG, polybutylene terephthalate (PBT), PTT or PEN; Described inorganic pore former is preferably carbonate, bicarbonate salts or soild oxide class, described carbonate is preferably calcium carbonate or sodium carbonate, and described soild oxide class is preferably silica, titanium dioxide, zinc oxide, tin oxide, magnesia or alundum (Al; Described pore former and hole-forming component weight ratio are 5: 95～70: 30, are preferably 10: 90～60: 40;
Described 25～200 ℃ of the draft temperatures that are stretched as of step b, draw ratio is 1.1～7 times, and draw speed is 1m/min～1000m/min, described being fixed to 100～250 ℃ of typings down, being preferably draft temperature is 30～150 ℃, draw ratio is 1.1～5 times, and draw speed is 5m/min～500m/min, and setting temperature is 170～220 ℃, more preferably draft temperature is 70～110 ℃, draw ratio is 2～4 times, and draw speed is 10m/min～300m/min, and setting temperature is 190～210 ℃.
The described solvent of pore former is a formic acid among the step c, benzene, toluene, dimethylbenzene, pentane, hexane, octane, cyclohexane, cyclohexanone, the toluene cyclohexanone, oxolane, chlorobenzene, dichloro-benzenes, carrene, chloroform, carbon tetrachloride, methyl alcohol, ethanol, isopropyl alcohol, ether, expoxy propane, methyl acetate, ethyl acetate, propyl acetate, acetone, butanone, espeleton, methylisobutylketone, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, phenol, ethylenediamine, decahydronaphthalene, biphenyl, dimethyl formamide, dimethyl sulfoxide (DMSO), dimethyl formamide, N-first class pyrrolidones, organic solvent or sulfuric acid such as metacresol, nitric acid, inorganic acids solvent and NaOH such as hydrochloric acid, any mixing of one or more of inorganic base solvents such as potassium hydroxide.
Described inorganic base also can comprise weak base such as sodium acid carbonate, saleratus, sodium carbonate, potash.
According to foregoing preparation method, behind step c, also carry out the aerobic heat cross-linking and handle, with further raising fiber film strength.
According to foregoing preparation method, described aerobic heat cross-linking is treated at 150～280 ℃ and handles 1min～80h down, is preferably at 180～250 ℃ and handles 1min～72h down, more preferably handles 1h～48h down at 200～230 ℃.
Technical scheme of the present invention has following advantage:
(1) owing to directly wrapped up supporting construction compound in the single fiber film, its intensity strengthens greatly, this tunica fibrosa can be used for the field that material tunica fibrosa of the same race can not be used.
(2) supporting construction can be coated on fibrous inside, and it can not decompose under any condition and scatter in conjunction with tightr.
(3) when adopting polyphenylene sulfide to make described tunica fibrosa, tunica fibrosa is acid and alkali-resistance, high temperature resistant more, and prolong service life greatly.
(4) hollow-fibre membrane that adopts the method for the invention to prepare, after it adopted heat cross-linking to handle, intermolecular combination was tightr, and tunica fibrosa intensity further is enhanced.
Description of drawings
Fig. 1 is the schematic cross-section of described hollow-fibre membrane, and wherein 1 is hole-forming component, and 2 for supporting component, and 3 is the aperture of hole-forming component;
Fig. 2 is the nozzle structure of the described hollow-fibre membrane of preparation, and wherein 21 are the ring-type injector hollow space for fused fiber ejection, the 22 tiny pipelines for the support component that is used to inject fusion.
The specific embodiment
Embodiment 1:
Hole-forming component: polyphenylene sulfide, pore former: copolyesters PET, support component: polyphenylene sulfide
Adopt the buss mixing roll, under 300 ℃, polyphenylene sulfide 9kg and 1kg copolyesters PET are carried out the blend granulation, prepare hole-forming component 10kg.Get support the pure polyphenylene sulfide 1kg of component and hole-forming component on composite spinning machine 310 ℃ extrude, carry out compoundly at 315 ℃, be prepared into 20: 80 composite polyphenylene sulfide doughnut of support component and the compound ratio of hole-forming component.This fiber is carried out drawing and setting handle 80 ℃ of draft temperatures, 4.5 times of draw ratios, draw speed 500m/min, 190 ℃ of setting temperatures; Then fiber is handled 24 hours with the molten water-soluble PET that goes in the hole-forming component in 20% sodium hydroxide lye down at 90 ℃, form hollow-fibre membrane.Then this hollow-fibre membrane is carried out aerobic heat treatment 10 minutes under 210 ℃, prepare the composite polyphenylene sulfide hollow-fibre membrane.This composite polyphenylene sulfide hollow-fibre membrane internal diameter 100 μ m, external diameter 350 μ m, film separates aperture 0.12～0.25 μ m, and percent opening 73% supports the component gross area and accounts for 18～22% of fabric integer cross-sectional area in the fiber cross section; Rupture strength 1.1MPa, fibre machinery intensity can be born 100kPa pressure, keep the grown form more than 18 minutes, soaking 10～12 days intensity forms in the various acid-base solutions remains unchanged, can be 200 ℃～220 ℃ long-term down in temperature uses, limited oxygen index is to be insoluble under 35～40%, 200 ℃ to appoint river solvent, pure water penetration speed 900L/m
3H (0.1MPa, 20 ℃).
Embodiment 2:
Hole-forming component: polyphenylene sulfide, pore former: silica, support component: polyphenylene sulfide
SiO 2 powder selects particle diameter at 5nm～200nm, the powder of preferred 5nm～50nm.Adopt double screw extruder, under 290 ℃, polyphenylene sulfide 9kg and 1kg silica are carried out the blend granulation, prepare hole-forming component 10kg.Get support the pure polyphenylene sulfide 1kg of component and hole-forming component on composite spinning machine 315 ℃ extrude, carry out compoundly at 320 ℃, be prepared into 10: 90 composite polyphenylene sulfide doughnut of support component and the compound ratio of hole-forming component.This fiber is carried out drawing and setting handle 90 ℃ of draft temperatures, 3.5 times of draw ratios, draw speed 600m/min, 200 ℃ of setting temperatures; Then fiber is at room temperature soaked 8 hours with the molten silica that goes in the hole-forming component in 10% potassium hydroxide solution, form hollow-fibre membrane.Then this hollow-fibre membrane is carried out aerobic heat treatment 50 hours under 185 ℃, prepare the composite polyphenylene sulfide hollow-fibre membrane.This composite polyphenylene sulfide hollow-fibre membrane internal diameter 300 μ m, external diameter 550 μ m, film separates aperture 0.08～0.18 μ m, and percent opening 80% supports the component gross area and accounts for 55～65% of fabric integer cross-sectional area in the fiber cross section; Rupture strength 1.2MPa, fibre machinery intensity can be born 120kPa pressure, keep the grown form more than 5～10 minutes, soaking 8～11 days intensity forms in the various acid-base solutions remains unchanged, can be 210 ℃～230 ℃ long-term down in temperature uses, limited oxygen index is to be insoluble under 35～40%, 200 ℃ to appoint river solvent, pure water penetration speed 980L/m
3H (0.1MPa, 20 ℃).
Embodiment 3:
Hole-forming component: polyphenylene sulfide, pore former: calcium carbonate, support component: polyphenylene sulfide;
Calcium carbonate powder selects particle diameter at 5nm～200nm, the powder of preferred 5nm～50nm.Adopt the buss screw rod, under 300 ℃, polyphenylene sulfide 9kg and 1kg calcium carbonate are carried out the blend granulation, prepare hole-forming component 10kg.Get support the pure polyphenylene sulfide 1kg of component and hole-forming component on composite spinning machine 315 ℃ extrude, carry out compoundly at 325 ℃, be prepared into 30: 70 composite polyphenylene sulfide doughnut of support component and the compound ratio of hole-forming component.This fiber is carried out drawing and setting handle 90 ℃ of draft temperatures, 3 times of draw ratios, draw speed 10m/min, 200 ℃ of setting temperatures; Then fiber is at room temperature soaked 4 hours with the molten calcium carbonate that goes in the hole-forming component in 10% aqueous hydrochloric acid solution, form hollow-fibre membrane.Then this hollow-fibre membrane is carried out aerobic heat treatment 50 hours under 225 ℃, prepare the composite polyphenylene sulfide hollow-fibre membrane.This composite polyphenylene sulfide hollow-fibre membrane internal diameter 400 μ m, external diameter 600 μ m, film separates aperture 0.12～0.2 μ m, and percent opening 70% supports the component gross area and accounts for 30～35% of fabric integer cross-sectional area in the fiber cross section; Rupture strength 1.1MPa, fibre machinery intensity can be born 100～115kPa pressure, keep the grown form more than 12～16 minutes, soaking 7～11 days intensity forms in the various acid-base solutions remains unchanged, can be 200 ℃～215 ℃ long-term down in temperature uses, limited oxygen index is to be insoluble under 37～40%, 200 ℃ to appoint river solvent, pure water penetration speed 960L/m
3H (0.1MPa, 20 ℃).
Embodiment 4:
Hole-forming component: polyphenylene sulfide, pore former: alundum (Al 50%+PA650%, support component: polyphenylene sulfide
The alundum (Al powder selects particle diameter at 5nm～200nm, the powder of preferred 5nm～50nm; PA6 selects inherent viscosity 2.3～3.5, and preferred 2.8～3.4.Adopt the buss screw rod, under 300 ℃, polyphenylene sulfide 6kg and 2kg alundum (Al, 2kg PA6 are carried out the blend granulation, prepare hole-forming component 10kg.Get support the pure polyphenylene sulfide 1kg of component and hole-forming component on composite spinning machine 310 ℃ extrude, carry out compoundly at 320 ℃, be prepared into 15: 85 composite polyphenylene sulfide doughnut of support component and the compound ratio of hole-forming component.This fiber is carried out drawing and setting handle 95 ℃ of draft temperatures, 3.7 times of draw ratios, draw speed 100m/min, 200 ℃ of setting temperatures; To soak 12 hours in the m-cresol solution of fiber under 50 ℃ then, again fiber is at room temperature soaked the alundum (Al of removing in the hole-forming component in 8 hours in 15% sodium hydrate aqueous solution, form hollow-fibre membrane with the molten PA6 that goes in the hole-forming component.Then this hollow-fibre membrane is carried out aerobic heat treatment 30 hours under 200 ℃, prepare the composite polyphenylene sulfide hollow-fibre membrane.This composite polyphenylene sulfide hollow-fibre membrane internal diameter 500 μ m, external diameter 800 μ m, film separates aperture 0.05～0.3 μ m, and percent opening 70% supports the component gross area and accounts for 5～7% of fabric integer cross-sectional area in the fiber cross section; Rupture strength 1.1MPa, fibre machinery intensity can be born 80～100kPa pressure, keep the grown form more than 7～12 minutes, soaking 5～10 days intensity forms in the various acid-base solutions remains unchanged, can be 180 ℃～230 ℃ long-term down in temperature uses, limited oxygen index is to be insoluble under 30～40%, 200 ℃ to appoint river solvent, pure water penetration speed 960L/m
3H (0.1MPa, 20 ℃).
Embodiment 5:
Hole-forming component: polyethylene, pore former: zinc oxide, support component: polypropylene
Zinc oxide powder selects particle diameter at 6nm～280nm, the powder of preferred 10nm～70nm.Adopt twin-screw, under 260 ℃, polyethylene 9.5kg and 0.5kg zinc oxide are carried out the blend granulation, prepare hole-forming component 10kg.Get support component virgin pp and hole-forming component on composite spinning machine 270 ℃ extrude, carry out compoundly at 275 ℃, be prepared into 20: 80 compound doughnut of support component and the compound ratio of hole-forming component.This fiber is carried out drawing and setting handle 60 ℃ of draft temperatures, 3.1 times of draw ratios, draw speed 1m/min, 120 ℃ of setting temperatures; Then fiber is at room temperature soaked the zinc oxide of removing in the hole-forming component in 8 hours in 15% aqueous hydrochloric acid solution, form hollow-fibre membrane.This composite hollow fiber membrane internal diameter 3～5 μ m, external diameter 8～20 μ m, film separates aperture 0.01～0.1 μ m, and percent opening 85～90% supports the component gross area and accounts for 10～15% of fabric integer cross-sectional area, pure water penetration speed 900L/m in the fiber cross section
3H (0.1MPa, 20 ℃).
Embodiment 6:
Hole-forming component: polyvinylidene fluoride, pore former: polyvinyl chloride, support component: PETG
It is 30,000～60,000 that polyvinyl chloride selects number-average molecular weight, preferred 40,000～50,000.Adopt screw rod, under 250 ℃, polyvinylidene fluoride 8kg and 2kg polyvinyl chloride are carried out the blend granulation, prepare hole-forming component 10kg.Get support the pure polystyrene of component and hole-forming component on composite spinning machine 275 ℃ extrude, carry out compoundly at 285 ℃, be prepared into 10: 90 compound doughnut of support component and the compound ratio of hole-forming component.This fiber is carried out drawing and setting handle 105 ℃ of draft temperatures, 4 times of draw ratios, 170 ℃ of setting temperatures; With soaking 12 hours in the cyclohexanone solution of fiber under 30 ℃, form hollow-fibre membrane then with the molten polyvinyl chloride that goes in the hole-forming component.This composite hollow fiber membrane internal diameter 10～50 μ m, external diameter 200～350 μ m, film separates aperture 0.2～1 μ m, and percent opening 75～80% supports the component gross area and accounts for 2～5% of fabric integer cross-sectional area, pure water penetration speed 990L/m in the fiber cross section
3H (0.1MPa, 20 ℃).
Embodiment 7:
Hole-forming component: nylon 66, pore former: silica supports component: polyphenylene sulfide
Adopt screw rod, under 300 ℃, nylon 66 8kg and 2kg silica are carried out the blend granulation, prepare hole-forming component 10kg.To support pure polyphenylene sulfide of component and hole-forming component on composite spinning machine 305 ℃ extrude, carry out compoundly at 310 ℃, be prepared into and support 15: 85 compound doughnut of component and the compound ratio of hole-forming component.This fiber is carried out drawing and setting handle 105 ℃ of draft temperatures, 7 times of draw ratios, draw speed 480m/min, 200 ℃ of setting temperatures; With soaking 12 hours in 10% salpeter solution of fiber under 50 ℃, form hollow-fibre membrane then with the molten silica that goes in the hole-forming component.Then this hollow-fibre membrane is carried out aerobic heat treatment 50 hours under 250 ℃, prepare composite hollow fiber membrane.This composite hollow fiber membrane internal diameter 100～200 μ m, external diameter 400～500 μ m, film separates aperture 0.5～2 μ m, and percent opening 30～35% supports the component gross area and accounts for 85～90% of fabric integer cross-sectional area, pure water penetration speed 850L/m in the fiber cross section
3H (0.1MPa, 20 ℃).
Embodiment 8:
Hole-forming component: polyether-ether-ketone, pore former: PEN, support component: polyether sulfone
Adopt twin-screw, under 380 ℃, polyether-ether-ketone 8kg and 5kg PEN are carried out the blend granulation, prepare hole-forming component 10kg.Get support the pure polyether sulfone 8kg of component and hole-forming component on composite spinning machine 400 ℃ extrude, carry out compoundly at 405 ℃, be prepared into 15: 85 compound doughnut of support component and the compound ratio of hole-forming component.This fiber is carried out drawing and setting handle 175 ℃ of draft temperatures, 2.7 times of draw ratios, draw speed 700m/min, 250 ℃ of setting temperatures; With soaking 12 hours in the phenol-tetrachloroethanes solution of fiber under 50 ℃, form hollow-fibre membrane then with the molten PEN that goes in the hole-forming component.Then this hollow-fibre membrane is carried out aerobic heat treatment 2 hours under 200 ℃, prepare composite hollow fiber membrane.This composite hollow fiber membrane internal diameter 700～850 μ m, external diameter 900～1000 μ m, film separates aperture 15～20 μ m, and percent opening 10～20% supports the component gross area and accounts for 45～50% of fabric integer cross-sectional area, pure water penetration speed 920L/m in the fiber cross section
3H (0.1MPa, 20 ℃).
Embodiment 9:
Hole-forming component: polyphenylene sulfide, pore former: tin oxide, support component: PEN
Stannic oxide powder selects particle diameter at 5nm～200nm, the powder of preferred 5nm～50nm.Adopt the buss screw rod, under 300 ℃, polyphenylene sulfide 6kg and 4kg tin oxide are carried out the blend granulation, prepare hole-forming component 10kg.Get support the pure PEN 14kg of component and hole-forming component on composite spinning machine 315 ℃ extrude, carry out compoundly at 320 ℃, be prepared into 15: 85 compound doughnut of support component and the compound ratio of hole-forming component.This fiber is carried out drawing and setting handle 105 ℃ of draft temperatures, 3.2 times of draw ratios, draw speed 5m/min, 190 ℃ of setting temperatures; Then fiber is at room temperature soaked the tin oxide of removing in the hole-forming component in 8 hours in 10% aqueous sulfuric acid, form hollow-fibre membrane.Then this hollow-fibre membrane is carried out aerobic heat treatment 1min under 150 ℃, prepare composite hollow fiber membrane.This composite hollow fiber membrane internal diameter 450～600 μ m, external diameter 700～800 μ m, film separates aperture 7～10 μ m, and percent opening 25～40% supports the component gross area and accounts for 55～60% of fabric integer cross-sectional area, pure water penetration speed 930L/m in the fiber cross section
3H (0.1MPa, 20 ℃).
Hollow-fibre membrane of the present invention also can be taked other embodiment preparations, for example support the composite material preparation that component adopts two or more material, when removing pore former, also can adopt other organic solvents, cited solvents of specification such as glycol monoethyl ether, ethylenediamine, decahydronaphthalene, biphenyl for example, it only is the simple replacement in concrete enforcement.
Described hollow-fibre membrane even can adopt wet method preparation, such as patent application CN200610015575 promptly discloses a kind of like this wet processing.And the concrete operations of wet processing also are conventionally known to one of skill in the art, and the present invention repeats no longer one by one.
Claims (10)
1. composite hollow fiber membrane, it is characterized in that, described composite hollow fiber membrane single fiber is by hole-forming component and support component and constitute, and described support component is continuous in the fiber axial directional distribution in composite hollow fiber membrane, is preferably described support component with the parallel distribution of fiber.
2. composite hollow fiber membrane according to claim 1 is characterized in that: described composite hollow fiber membrane surface apertures is 0.01～20 μ m, and surperficial percent opening is 10～90%, and film external diameter 8～1000 μ m, film internal diameter are 3～900 μ m; Being preferably surface apertures is 0.1～10 μ m, and surperficial percent opening is 20～80%; Film external diameter 10～900 μ m, film internal diameter are 5～800 μ m; More preferably surface apertures is 0.2～0.3 μ m, and surperficial percent opening is 25～40%; Film external diameter 20～350 μ m, film internal diameter are 10～300 μ m.
3. composite hollow fiber membrane according to claim 1 is characterized in that: described hole-forming component is one or more any combinations in the thermoplastic resin material, wherein is preferably polyphenylene sulfide.
4. composite hollow fiber membrane according to claim 1 is characterized in that: described support group is divided into one or more any combinations in the thermoplastic resin material, wherein is preferably polyphenylene sulfide.
5. composite hollow fiber membrane according to claim 1 is characterized in that: described composite hollow fiber membrane is formed by compound extruding after supporting component and the other fusion of hole-forming component.
6. composite hollow fiber membrane according to claim 1 is characterized in that: described support component weight content is 2～90% of a tunica fibrosa gross weight, is preferably 5%～85%, more preferably 10～80%.
7. the preparation method of any described composite hollow fiber membrane of claim 1～6 is characterized in that: comprise the steps:
A, with hole-forming component and pore former blend granulation, then with support component compound extruding after the fusion respectively, obtain compound doughnut;
B, the compound compound doughnut that obtains stretched and thermal finalization is handled;
C, the compound doughnut after the stretching thermal finalization is removed pore former in solvent, obtain composite hollow fiber membrane.
8. preparation method according to claim 7 is characterized in that:
Step a is described to be extruded to adopting screw extruder to extrude, described extruding under 100～450 ℃, extruding, described compound be down compound at 110～450 ℃, be preferably under 290～345 ℃ and extrude, compound down at 295～350 ℃, more preferably under 300～330 ℃, extrude, compound down at 305～330 ℃; Described pore former comprises organic pore former and inorganic pore former; That described organic pore former is preferably is polyamide-based, TPO or polyesters, described polyamide-based nylon 6 or the nylon 66 of being preferably, described TPO is preferably polyethylene, polyvinyl chloride, polystyrene or polypropylene, and described polyesters is preferably PETG, polybutylene terephthalate (PBT), PTT or PEN; Described inorganic pore former is preferably carbonate, bicarbonate salts or soild oxide class, described carbonate is preferably calcium carbonate or sodium carbonate, and described soild oxide class is preferably silica, titanium dioxide, zinc oxide, tin oxide, magnesia or alundum (Al; Described pore former and hole-forming component weight ratio are 5: 95～70: 30, are preferably 10: 90～60: 40;
Described 25～200 ℃ of the draft temperatures that are stretched as of step b, draw ratio is 1.1～7 times, and draw speed is 1m/min～1000m/min, described being fixed to 100～250 ℃ of typings down, being preferably draft temperature is 30～150 ℃, draw ratio is 1.1～5 times, and draw speed is 5m/min～500m/min, and setting temperature is 170～220 ℃, more preferably draft temperature is 70～110 ℃, draw ratio is 2～4 times, and draw speed is 10m/min～300m/min, and setting temperature is 190～210 ℃.
The described solvent of pore former is organic solvent, inorganic acid or inorganic base among the step c; Described organic solvent preferable formic acid, benzene, toluene, dimethylbenzene, pentane, hexane, octane, cyclohexane, cyclohexanone, the toluene cyclohexanone, oxolane, chlorobenzene, dichloro-benzenes, carrene, chloroform, carbon tetrachloride, methyl alcohol, ethanol, isopropyl alcohol, ether, expoxy propane, methyl acetate, ethyl acetate, propyl acetate, acetone, butanone, espeleton, methylisobutylketone, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, phenol, ethylenediamine, decahydronaphthalene, biphenyl, dimethyl formamide, dimethyl sulfoxide (DMSO), dimethyl formamide, N-first class pyrrolidones, the any combination of in the metacresol one or more; Described inorganic acid is preferably one or more any combinations in sulfuric acid, nitric acid, the hydrochloric acid; One or more any combinations in the preferred NaOH of described inorganic base, the potassium hydroxide.
9. according to claim 7 or 8 described preparation methods, it is characterized in that: behind step c, also carry out the aerobic heat cross-linking and handle.
10. preparation method according to claim 9, it is characterized in that: described aerobic heat cross-linking is treated at 150～280 ℃ and handles 1min～80h down, be preferably at 180～250 ℃ and handle 1min～72h down, more preferably handle 1h～48h down at 200～230 ℃.
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