CN1883779A - Process for preparing composite hollow fiber membrane - Google Patents
Process for preparing composite hollow fiber membrane Download PDFInfo
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- CN1883779A CN1883779A CN 200610035536 CN200610035536A CN1883779A CN 1883779 A CN1883779 A CN 1883779A CN 200610035536 CN200610035536 CN 200610035536 CN 200610035536 A CN200610035536 A CN 200610035536A CN 1883779 A CN1883779 A CN 1883779A
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Abstract
A preparation of composite hollow fiber membrane adopts solution phase transfer hollow fiber spinning process, makes poly(ethylene terephthalate) or polysulfone, solvent and pore-forming agent into a base membrane spinning solution of composite hollow fiber membrane, makes polyvinylidene fluoride or other copolymers or mixture of same, solvent and pore-forming agent into composite layer spinning solution of composite hollow fiber membrane and simultaneously extrudes the said two spinning solution and core solution in the hole of the spinneret central pipe through the spinneret for outside condensation bath. The solvents and pore-forming agents in the two kinds of spinning solutions prepared in said step (1) and (2) enters condensation solution phase and the polymers, as the composite layer and the base membrane materials, precipitates into polymer hollow fiber membrane due to phase transfer, producing high-strength and high-flux hydrophilic composite hollow fiber membrane.
Description
Technical field
The present invention relates to a kind of preparation method of composite hollow fiber membrane, particularly relate to the preparation method of a kind of high strength, the compound doughnut perforated membrane of high-throughout hydrophily.
Background technology
Hollow-fibre membrane is mainly used in filtration or the dialysis in the various fields.The design of employing composite membrane can be studied respectively with selection and separate composite bed membrane material and basal lamina material, is easy to obtain the diffusion barrier of high score from function, high permeation flux, and therefore, composite membrane technology has become important development direction in the high functional membrane technology of preparing.
This technology develops the earliest and is applied to reverse osmosis membrane, gas separation membrane system.A major issue is that the film pollution causes the film permeation flux to be decayed significantly in the milipore filter practical application, by charged modification or hydrophilically modified, can improve the resistance tocrocking of membrane material, but along with the modification degree increases, often cause membrane material intensity to weaken, especially for hollow-fibre membrane, film-strength is provided by separation membrane material self fully, the practicality of diffusion barrier is not only relevant with separation function, simultaneously closely related with film-strength, this has just limited selection and the study on the modification of high score from functional film material greatly.Therefore, along with the development of application of membrane, composite membrane technology has also entered the research of milipore filter.For little porous ultrafiltration membrane, membrane structure is comparatively fine and close usually simultaneously, and it is bigger that film sees through resistance, and by complex technique, basement membrane can adopt the comparatively big porous ultrafiltration membrane of vegetables pine of structure, thereby is expected to obtain high-throughout little porous ultrafiltration membrane.Equally, for big porous ultrafiltration membrane and microporous barrier, basement membrane can adopt film to see through the littler microporous barrier of resistance, is expected to obtain the high functional membrane of high score from function, high permeation flux, high resistance tocrocking, high working strength by complex technique.In addition,, the consumption of high score can be reduced, also the membrane material cost can be reduced from function modified membrane material owing to adopt complex technique.Because it is the highest that the hollow fiber type diffusion barrier has the film loading density, but advantages such as backwash, introduce complex technique, make the hollow fiber separating film higher functionization, has important Practical significance, therefore, the composite hollow fiber membrane technology is the current research focus of domestic and international high function hollow-fibre membrane development.
Early stage composite hollow fiber membrane technology is on the hollow-fibre membrane surface that has been shaped, adopts solution coated method or surface reaction to form composite membrane, and research all has report both at home and abroad in this respect.Its shortcoming is: 1. composite and solvent range of choice are narrow; 2. aftertreatment technology is had relatively high expectations; 3. it is wayward to separate the aperture.Therefore this method is mainly used in the dense film of preparation in the past, as gas separation membrane, reverse osmosis membrane, NF membrane etc.
The radially section structure of doughnut perforated membrane is generally unsymmetric structure, promptly form by selective separating and porous support layer, but because the polyvinylidene fluoride resin surface can be very low, hydrophobicity is stronger, form fluid-tight compactness cortex during the spinning hollow-fibre membrane easily, thereby lost the filtering function that the doughnut perforated membrane should have.
Along with constantly bringing forth new ideas of masking technique, people utilize the method for adding various pore former and auxiliary agent in spinning solution to solve the problems referred to above, and disclosed pertinent literature is as follows:
(1) among the public clear 62-017614 of this spy, mixing Kynoar, macromolecule pore former polyethylene glycol, surfactant Tween-80 have been put down in writing, the method for phase transfer film forming then.The product rupture strength deficiency that this method obtained, the penetration speed of pure water is slower, can't satisfy the demand.
(2) among this special fair 3-71168, put down in writing the preparation method of the polyethylene glycol of adding 7.2wt%, but still failed to obtain the film of high permeation flux as pore former.
(3) put down in writing the method for Kynoar, solvent, macromolecule pore former, non-solvent, surfactant etc. being mixed the back film forming among the N1128176A.Wherein macromolecule pore former, non-solvent, the surfactant that adds with proper proportion, even cosolvent, they interact, and coordinate mutually, obtain the hollow membrane of high permeation flux; But shortcoming is to be difficult to obtain high strength, high-throughout film product.
(4) put down in writing among the N1265048A Kynoar, organic liquid and inorganic granular mixing, melt spinning obtains the hollow-fibre membrane that internal diameter is big, be suitable for high viscosity liquid then.But the shortcoming of this method remains and is difficult to obtain high strength, high-throughout film product.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of composite hollow fiber membrane, adopt conventional dissolving, to in organic solvent, mix as polymer, the pore former of basal lamina material and composite material, carry out wet method or dry-wet spinning, by phase transfer, make high strength, the compound doughnut perforated membrane of high-throughout hydrophily.
Purpose of the present invention can realize by following technical measures, and a kind of preparation method of composite hollow fiber membrane adopts solution phase transfer doughnut spinning technique, it is characterized in that described preparation method may further comprise the steps:
(1). polyether sulfone or polysulfones, solvent, pore former are mixed in following ratio:
Polyether sulfone or polysulfones 10～40wt%;
Solvent 50～80wt%;
Pore former 2～40wt%;
Above-mentioned solution stirring and dissolving is even, make the basement membrane spinning solution of composite hollow fiber membrane;
(2). Kynoar or its copolymer or the mixture of the two, solvent, pore former are mixed in following ratio:
Kynoar or its copolymer or the mixture 10～40wt% of the two;
Solvent 50～80wt%;
Pore former 2～40wt%;
Above-mentioned solution stirring and dissolving is even, make the composite bed spinning solution of composite hollow fiber membrane;
(3). above-mentioned two kinds of spinning solutions are extruded simultaneously by the spinning head and the core liquid in the pore of spinning head center of doughnut spinning-drawing machine, enter then in the outer coagulating bath, solvent in two kinds of spinning solutions that make in above-mentioned steps (1), (2) and pore former enter and solidify liquid phase, and as the polymer of composite bed and basal lamina material because phase transfer and precipitating becomes the polymer hollow-fibre membrane, thereby be spun into the composite hollow fiber membrane that comprises composite bed and basement membrane.
Described basement membrane is called supporting layer again, and above-mentioned basal lamina material is selected the higher conventional material of preparing of mechanical strength such as polyether sulfone or polysulfones for use, is preferably polyether sulfone.
Described composite material can also be a kind of mixture that mixes in a kind of and following polymer in Kynoar and its copolymer: polymethyl methacrylate, polyvinyl alcohol, polyvinyl acetate, polyacrylonitrile, Pioloform, polyvinyl acetal etc., the total content that composite material accounts for the composite bed spinning solution is constant.
Described polyvinylidene fluoride alkene copolymer is no less than 60% copolymer for the vinylidene repetitive.
The solvent that pore former and polymer are dissolved in used being used in described basement membrane spinning solution or the composite bed spinning solution is preferably intensive polar solvent, can think the mixture of following one or more solvents: dimethyl formamide (DMF), dimethylacetylamide (DMAc), N-methyl pyrrolidone, triethyl phosphate, sulfolane, dimethyl sulfoxide (DMSO) etc.
Described core liquid can be water or other non-solvent, be suitable for spinning composite material in the composite hollow fiber membrane inboard, basal lamina material is at the inner pressed composite hollow fiber membrane in the composite hollow fiber membrane outside.
The core liquid that described spinning is used can also be the mixed liquor of water and an amount of spin solvent, be suitable for spinning composite material in the composite hollow fiber membrane outside, basal lamina material is at the external-compression type composite hollow fiber membrane of composite hollow fiber membrane inboard.
Outer coagulating bath described in the above-mentioned steps (3) is water or other non-solvent.
Described pore former can be inorganic pore former or organic polymer pore former or be the mixture of the two.
Described inorganic pore former is following one or more mixture: lithium nitrate, sodium chloride, calcium chloride, calcium carbonate, calcium nitrate, silica, alundum (Al, kaolin etc.The content of inorganic pore former in composite bed or basement membrane spinning solution is 0.5～20wt%, is preferably 1～10wt%, and the granularity of inorganic pore former is less than 10 microns, and it is preferably nanometer particle.
When adopting inorganic pore former, can after spinning, use alkali, acid, water or organic solvent etc. again with the pore former stripping.
Described organic polymer pore former is following one or more mixture: water soluble polymers such as polyethylene glycol, polyoxyethylene, polyvinylpyrrolidone, polyvinyl alcohol, methylcellulose, wherein, the molecular weight of polyethylene glycol is preferably 200～20000 dalton, polyoxyethylated molecular weight is preferably 100,000 dalton or bigger, and the molecular weight of polyvinylpyrrolidone is preferably 10,000～1,200,000 dalton.The content of organic polymer pore former in composite bed or basement membrane spinning solution is 2～30wt%, is preferably 5～20wt%.
The present invention can further improve, in order to improve the surface tension of polymer spinning solution, improve spinning solution viscosity, leave standstill stability and doughnut pore-creating character, various system film additives are carried out composite processing.Except above-mentioned adding the pore former in spinning solution, described system film additive can also comprise surfactant and other additive.
Described surfactant is following one or more mixture: cationic surface active agent, anionic surfactant, amphoteric surfactant, nonionic surface active agent.As: lauryl sodium sulfate, neopelex, softex kw, secondary octanol APEO, dodecyl sulfamic acid sodium, fluorine-containing surfactant, Tween-20, Tween-80 etc.
The content of described surfactant in composite bed or basement membrane spinning solution is 0.01～5wt%, and at this moment, the content of the pore former in above-mentioned two spinning solutions is 2～39wt%.
Surfactant is also different according to the addition that its kind does not coexist in above-mentioned two spinning solutions, is preferably 1～2wt% as common nonionic surface active agent addition, and the fluorine-containing surfactant addition is preferably 0.05～0.5wt%.
The present invention can do following improvement, also can add cosolvent in described two kinds of spinning solutions, as dioxane, butanone etc., to adjust the dissolved state of spinning solution.Cosolvent is as the part of solvent, and the total content in any spinning solution is 1～4wt% therein.
Adopt the preparation method of composite hollow fiber membrane of the present invention, the composite hollow fiber membrane that makes, its external diameter is 0.3～3mm, wall thickness is 0.05～1mm, and porosity is 50～90%, and it is 0.01～1 micron that film separates the aperture, rupture strength is 0.6～2MPa, at 0.1MPa, under 25 ℃ the test condition, the pure water water flux is 600～10000L/m
2H.
The composite bed of described composite hollow fiber membrane is 1: 50～2: 1 with the ratio of the thickness of basement membrane, is preferably 1: 10～1: 1, can realize by the feed amount of adjusting two kinds of spinning solutions according to actual needs.
The described composite hollow fiber membrane that spins out can stretch 100～300% again, thereby further improves the water flux of Kynoar doughnut membrane porosity and hollow-fibre membrane.
Compared with prior art, beneficial effect of the present invention is as follows:
The preparation method of composite hollow fiber membrane of the present invention has adopted composite membrane technology, can spin out stable performance, suitable, the high water flux in aperture and high-intensity composite hollow fiber membrane.Because a little less than the PVDF membrane material mechanical strength, but it has excellent antifouling property, demonstrates excellent performance at high pollution separation systems such as sewage disposal, biochemical pharmacy industries; The antifouling property of membrane material such as polyether sulfone or polysulfones is not as Kynoar, but it has the favorable mechanical performance, so with Kynoar etc. as composite material, contact with separating liquid, separation function is provided, polyether sulfone or polysulfones etc. provide the mechanical strength that meets instructions for use as backing material, and the performance of two kinds of materials is complementary just.
Advantage of the present invention is: 1. solvent is easy to select, and composite bed membrane material range of choice enlarges; 2. composite bed thickness is easy to stable control; 3. film separation aperture is easy to select and control; 4. combination process is simple, directly enter the wet spinning of coagulating bath water tank after can adopting spinning solution to come out, also can adopt spinning solution after spinning nozzle comes out, air, to enter coagulating bath water tank behind the travel distance again and do a wet spinning through one section from spinning nozzle; 5. film-strength and film separation function height.By changing the hollow fiber composite membrane that composite bed membrane material prescription and basal lamina material prescription, spinning technology parameter and doughnut post-treatment condition can obtain certain pore size.This method can be used to develop various high function milipore filters, micro-filtration membrane, NF membrane and gas separation membrane etc.
Below by the test example, beneficial effect of the present invention is further specified.
In the following test example, described " feed than " is basal lamina material and the feed ratio of composite material; The composite fibre external diameter is meant total external diameter of composite membrane; Thickness is the gross thickness of composite hollow fiber membrane.
Experimental example 1: the THICKNESS CONTROL of composite hollow fiber membrane composite bed
The control of table 1 inner pressed composite membrane composite bed thickness
| Numbering | Total feed amount ml/min | The feed ratio | Hauling speed m/min | The interior liquid measure ml/min that injects | Composite fibre external diameter mm | Thickness mm |
| 1 | 14.4 | 40∶40 | 16.3 | 18.3 | 1.38 | 0.30 |
| 2 | 14.4 | 50∶30 | 16.3 | 18.3 | 1.38 | 0.30 |
| 3 | 14.4 | 60∶20 | 16.3 | 18.3 | 1.38 | 0.30 |
| 4 | 14.4 | 70∶10 | 16.3 | 18.3 | 1.38 | 0.30 |
| 5 | 14.4 | 75∶5 | 16.3 | 18.3 | 1.38 | 0.30 |
| 6 | 14.4 | 80∶0 | 16.3 | 18.3 | 1.38 | 0.30 |
Annotate: the composite membrane prescription is with embodiment 1;
Experimental example 2
The control of table 2 external-compression type composite hollow fiber membrane composite bed thickness
| Numbering | The feed ratio | Fracture pressure MP | Permeation flux L/m 2.hr | Rejection % | |
| Ovalbumin (4.5 ten thousand) | Pepsin (3.5 ten thousand) | ||||
| 1 | 0∶60 | 0.30 | 27.3 | ＞90 | 90 |
| 2 | 30∶30 | 0.53 | 112 | ＞90 | 90 |
| 3 | 40∶20 | 0.65 | 129 | ＞90 | 90 |
| 4 | 50∶10 | 0.70 | 154 | ＞90 | 90 |
| 5 | 60∶0 | 0.75 | 83.6 | 95 | - |
Annotate: the composite membrane prescription is with embodiment 2;
Total feed amount is 10.8ml/min, and hauling speed is 30m/min, and the core liquid measure is 41.7ml/min, and the composite fibre external diameter is for being 0.9mm, and thickness is 0.15mm;
Can find out by table 1, table 2,, can control the thickness of composite bed in the composite membrane hollow-fibre membrane easily, promptly control the relative thickness of composite bed by the change of spinning membrane system stoste feed ratio.Can see that from the microscopic examination fiber cross sections resulting film is compound evenly, illustrates that the compound control of this composite membrane is simple for process.
From the radially microscopic examination of section of doughnut, form angle from material, two kinds of materials of basement membrane and composite bed respectively form an annulus; From material geometry angle, surface compact layer, porous support layer etc. are arranged.By THICKNESS CONTROL, make the composite bed membrane material, very thin as Kynoar, only belong to compacted zone; Or thicker, compacted zone and partially porous layer material all are Kynoar.
As shown in Table 2, composite hollow fiber membrane to hold back aperture and composite bed thickness irrelevant.The separation aperture of only depending on the composite bed membrane material.But permeation flux is the size that sees through resistance of film then depends on composite bed resistance and basement membrane resistance sum.Because compound tunic sees through resistance and sees through resistance (this point is determined by the composite membrane design principle: basement membrane provides the main intensity of film, and composite bed provides centrifugation) greater than basement membrane, so along with the reduction of composite membrane thickness, the increase of film permeation flux.Because the composite bed film strength is weaker than basement membrane, so reduce the also corresponding raising of film-strength along with composite bed thickness.
Composite bed is depended in the separation aperture that is composite hollow fiber membrane, but irrelevant with composite bed thickness, on the contrary, the thickness that composite bed is relative is more little, and the mechanical strength of film is big more.This meets the desired design purpose of composite membrane fully.
Test example 3: the different composite layer formula separates the influence in aperture on the basement membrane to film
Table 3 basement membrane is to the influence of composite membrane aperture control
| Film is formed | Water flux L/m 2·hr | Rejection % | |||
| PEG-200 00 | Pepsin (3.5 ten thousand) | Ovalbumin (4.5 ten thousand) | Bovine serum albumin (6.7 ten thousand) | ||
| Preparation liquid A+ basement membrane | 112 | - | 90 | 99 | - |
| Preparation liquid C+ basement membrane | 120 | - | - | 70 | 96 |
| Preparation liquid D+ basement membrane | 92 | 30 | 90 | - | - |
| Preparation liquid E+ basement membrane | 83 | 50 | - | - | |
| Preparation liquid F+ basement membrane | 43 | 70 | 95 | - | - |
| Preparation liquid A | 27 | - | - | - | - |
| Basement membrane | 84 | - | - | 95 | - |
Annotate: above-mentioned composite membrane is the external-compression type film, external diameter is 0.9mm, internal diameter is 0.6mm, compound feed ratio is 1: 1, and hauling speed is 30m/min, and bee line is 10cm, core liquid is the 50V%DMF aqueous solution, the feed amount of core liquid is 41.7ml/min, and total feed amount is 10.8ml/min, and the PEG-20000 in the table is a Macrogol 2000 0.
Multiple field film for the external-compression type hollow-fibre membrane is held back the face structure, can be by the control of the promptly interior solidification liquid condition of core liquid, the internal dense lamella aperture of basement membrane is increased, structure is comparatively loose, and the outer compacted zone of basement membrane is then replaced by the composite bed membrane material makes the separation aperture depend on outer compactness composite film material.Like this, still can be used as the basement membrane of holding back the bigger composite bed membrane material in aperture for the former less film in aperture of holding back, be because the control of composite bed, the outer compacted zone aperture of basement membrane is increased, greater than the separation aperture of composite bed membrane material, like this, can adopt the better basement membrane of intensity and do not influence composite membrane totally hold back the aperture, for common polysulfones, polyether sulfone hollow-fibre membrane, it is more little that it holds back the aperture, and film-strength is high more.
By table 3 data as can be known, on same basement membrane, along with composite membrane is held back the increase in aperture, the also corresponding increase of composite hollow fiber membrane water permeation flux illustrates that this basement membrane does not influence the aperture of holding back of composite membrane for the composite hollow fiber membrane of different composite prescription.See simultaneously, when the basement membrane prescription spinned hollow-fibre membrane separately, the water permeation flux of film was less than the flux of part composite membrane, and this can be explained by above-mentioned analysis, be that the main resistant layer of former basement membrane---outer compacted zone is replaced by composite bed, and the composite bed membrane structure is a cavernous structure.Usually the membrane resistance and the film thickness relation that have the finger-like pore structural membrane are not very big, resistance is mainly from thin compacted zone, and the membrane resistance of cavernous structure film and thickness have direct relation: be that thickness is more little generally speaking, resistance is more little, and is also relevant with the compactness of cavernous body in addition.Generally speaking, when composite bed was very thin, then resistance was very little, permeation flux is big).So just making that basement membrane spins the permeation flux of film forming separately can be less than the permeation flux of part composite membrane.
The specific embodiment
Further describe the present invention with embodiment below, it does not limit protection scope of the present invention.
Adopt solution phase transfer doughnut spinning technique commonly used in the prior art (wet method or dried-wet method) condition system film.
Embodiment 1
Under 500 gram calcium carbonate, 2 micro particles high-speed stirred, be dispersed in 5 kilograms of dimethylacetylamides, add 2 kilograms of dimethylacetylamides again, 2 kilograms of polyvinylidene fluoride resins, 500 gram polyethylene glycol, 100 restrain Tween-20s, stirring and dissolving is even, makes doughnut composite bed spinning solution.With 7 kilograms of dimethylacetylamides, 2 kilograms of polyethersulfone resins, 500 gram polyethylene glycol, stirring and dissolving is even, makes doughnut basement membrane spinning solution.Adopt and do-wet method doughnut spinning technique, two kinds of spinning solutions and core liquid (core liquid is the 70v%DMA aqueous solution) are extruded simultaneously by the composite spinning spout,, draw on wire wrapping wheel, form compound doughnut through outer coagulating bath water tank.Coagulating agent is a water in the outer coagulating bath.Remove calcium carbonate in the Kynoar doughnut, the external pressure Kynoar doughnut composite porous film that obtains with hydrochloric acid solution.External diameter 1.04mm, wall thickness 0.20mm, the thick 0.08mm of Kynoar cortex wherein, rupture strength 0.92MPa, at 0.1Mpa, under 20 ℃ the test condition, pure water penetration speed 970L/m
2H, film separates aperture 0.10 μ m, porosity 72%.
Comparative example 1: under 500 gram calcium carbonate, 2 micro particles high-speed stirred, be dispersed in 5 kilograms of dimethylacetamide solvents, add 2 kilograms of dimethylacetylamides again, 2 kilograms of polyvinylidene fluoride resins, 500 gram polyethylene glycol, 100 restrain soil temperatures-20, stirring and dissolving is even, spinning, coagulating agent is a water in the coagulating bath.The external pressure Kynoar doughnut perforated membrane external diameter 1.04mm that obtains, wall thickness 0.20mm, rupture strength 0.42MPa, pure water penetration speed 950L/m
220 ℃ of h@0.1MPa, film separates aperture 0.10 μ m, porosity 75%.
Embodiment 2
500 gram alundum (Als, 20～80 nanoparticles at high speed are stirred down, be dispersed in 7 kilograms of N-crassitude ketone solvents, add 2 kilograms of polyvinylidene fluoride resins, 500 gram polyvinylpyrrolidones, 100 gram Tween-80s again, stirring and dissolving is even, makes doughnut cortex spinning solution.With 7 kilograms of dimethylacetylamides, 2 kilograms of polyethersulfone resins, 500 gram polyethylene glycol, stirring and dissolving is even, makes doughnut supporting layer spinning solution.Adopt and do-wet method doughnut spinning technique, two kinds of spinning solutions and core liquid (core liquid is the 70v%DMA aqueous solution) are extruded simultaneously by the composite spinning spout,, draw on wire wrapping wheel, form compound doughnut through outer coagulating bath water tank.Coagulating agent is a water in the coagulating bath.Remove alundum (Al in the Kynoar doughnut with the NaOH aqueous solution, the external pressure Kynoar doughnut perforated membrane external diameter 0.5mm that obtains, wall thickness 0.15mm, the thick 0.05mm of Kynoar cortex wherein, rupture strength 0.62MPa, at 0.1Mpa, under 20 ℃ the test condition, pure water penetration speed 1270L/m
2H, film separates aperture 0.20 μ m, porosity 78%.
Comparative example 2: 500 gram alundum (Als, 20～80 nanoparticles at high speed are stirred down, be dispersed in 7 kilograms of N-crassitude ketone solvents, add 2 kilograms of polyvinylidene fluoride resins, 500 gram polyvinylpyrrolidones, 100 gram Tween-80s again, stirring and dissolving is even, spinning, coagulating agent is a water in the coagulating bath.The external pressure Kynoar doughnut perforated membrane internal diameter 0.5mm that obtains, wall thickness 0.15mm, rupture strength 0.32MPa, pure water penetration speed 1280L/m
220 ℃ of h@0.1MPa, film separates aperture 0.20 μ m, porosity 77%.
Embodiment 3
Under 800 gram calcium carbonate, 2 micro particles high-speed stirred, be dispersed in 5 kilograms of dimethylacetylamides, add 1.8 kilograms of dimethylacetylamides again, 1.8 kilogram polyvinylidene fluoride resin, 780 gram polyvinylpyrrolidones, 20 gram fluorine FC-4, stirring and dissolving is even, makes doughnut cortex spinning solution.With 7 kilograms of dimethylacetylamides, 2 kilograms of polyethersulfone resins, 500 gram polyethylene glycol, stirring and dissolving is even, makes doughnut supporting layer spinning solution.Adopt and do-wet method doughnut spinning technique, two kinds of spinning solutions and core liquid water are extruded simultaneously by the composite spinning spout,, draw on wire wrapping wheel, form compound doughnut through outer coagulating bath water tank.Coagulating agent is a water in the coagulating bath.Remove calcium carbonate in the Kynoar doughnut with hydrochloric acid solution.At 0.1Mpa, under 20 ℃ the condition, the interior pressure Kynoar doughnut perforated membrane internal diameter 0.8mm that obtains, wall thickness 0.30mm, the thick 0.08mm of Kynoar cortex wherein, rupture strength 0.93MPa, pure water penetration speed 1310L/m
2H, film separates aperture 0.50 μ m, and porosity is 81%.
Embodiment 4
Under 2 kilograms of polyvinylidene fluoride resin high-speed stirred, be dispersed in 7 kilograms of dimethylacetylamides, add 500 gram Macrogol 6000s, 100 gram Tween-20s again, stirring and dissolving is even, makes doughnut composite bed spinning solution.With 7 kilograms of dimethylacetylamides, 2 kilograms of polyethersulfone resins, 500 gram polyethylene glycol, stirring and dissolving is even, makes doughnut basement membrane spinning solution.Adopt and do-wet method doughnut spinning technique, two kinds of spinning solutions and core liquid (core liquid is the 70v%DMA aqueous solution) are extruded simultaneously by the composite spinning spout,, draw on wire wrapping wheel, form compound doughnut through outer coagulating bath water tank.Coagulating agent is a water in the outer coagulating bath.Remove calcium carbonate in the Kynoar doughnut, the external pressure Kynoar doughnut composite porous film that obtains with hydrochloric acid solution.External diameter 1.04mm, wall thickness 0.20mm, the thick 0.08mm of Kynoar cortex wherein, rupture strength 0.95MPa, at 0.1Mpa, under 20 ℃ the test condition, pure water penetration speed 470L/m
2H, film separates aperture 0.04 μ m, porosity 70%.
Comparative example 4: under 2 kilograms of polyvinylidene fluoride resin high-speed stirred, be dispersed in 7 kilograms of dimethylacetamide solvents, add 500 gram polyethylene glycol, 100 gram Tween-20s again, stirring and dissolving is even, spinning, and coagulating agent is a water in the coagulating bath.The external pressure Kynoar doughnut perforated membrane that obtains, external diameter 1.04mm, wall thickness 0.20mm, rupture strength 0.47MPa, pure water penetration speed 480L/m
220 ℃ of h@0.1MPa, film separates aperture 0.04 μ m, porosity 72%.
Embodiment 5
Under 2 kilograms of polyvinylidene fluoride resin high-speed stirred, be dispersed in 7 kilograms of dimethylacetylamides, add 2000 gram Macrogol 6000s, 400 gram Tween-20s again, stirring and dissolving is even, makes doughnut composite bed spinning solution.With 7 kilograms of dimethylacetylamides, 2 kilograms of polyethersulfone resins, 1500 gram polyethylene glycol, stirring and dissolving is even, makes doughnut basement membrane spinning solution, and core liquid is the 70v%DMA aqueous solution.Adopt and do-wet method doughnut spinning technique, two kinds of spinning solutions and core liquid are extruded simultaneously by the composite spinning spout,, draw on wire wrapping wheel, form compound doughnut through outer coagulating bath water tank.Coagulating agent is a water in the outer coagulating bath.Remove calcium carbonate in the Kynoar doughnut with hydrochloric acid solution, the external pressure Kynoar doughnut composite porous film that obtains, its external diameter is 1.04mm, wall thickness 0.20mm, the thick 0.08mm of Kynoar cortex wherein, rupture strength 0.85MPa is at 0.1Mpa, under 20 ℃ the test condition, pure water penetration speed 670L/m
2H, film separates aperture 0.08 μ m, porosity 70%.
Comparative example 5: under 2 kilograms of polyvinylidene fluoride resin high-speed stirred, be dispersed in 7 kilograms of dimethylacetamide solvents, add 2000 gram polyethylene glycol, 400 gram Tween-20s again, stirring and dissolving is even, spinning, and coagulating agent is a water in the coagulating bath.The external pressure Kynoar doughnut perforated membrane that obtains, external diameter 1.04mm, wall thickness 0.20mm, rupture strength 0.38MPa, pure water penetration speed 780L/m
220 ℃ of h@0.1MPa, film separates aperture 0.08 μ m, porosity 72%.
Embodiment 6
Under 2 kilograms of polyvinylidene fluoride resin high-speed stirred, be dispersed in 7 kilograms of dimethylacetylamides, add 500 gram Macrogol 6000s, 100 gram Tween-20s again, stirring and dissolving is even, makes doughnut composite bed spinning solution.With 7 kilograms of dimethylacetylamides, 2 kilograms of polyethersulfone resins, 500 gram polyethylene glycol, stirring and dissolving is even, makes doughnut basement membrane spinning solution, and core liquid is the 70v%DMA aqueous solution.Adopt and do-wet method doughnut spinning technique, two kinds of spinning solutions and core liquid are extruded simultaneously by the composite spinning spout,, draw on wire wrapping wheel, form compound doughnut through outer coagulating bath water tank.Coagulating agent is a water in the outer coagulating bath.Remove calcium carbonate in the Kynoar doughnut, the external pressure Kynoar doughnut composite porous film that obtains with hydrochloric acid solution.External diameter 1.04mm, wall thickness 0.20mm, the thick 0.08mm of Kynoar cortex wherein, rupture strength 0.95MPa, at 0.1Mpa, under 20 ℃ the test condition, pure water penetration speed 470L/m
2H, film separates aperture 0.04 μ m, porosity 70%.
Claims (9)
1. the preparation method of a composite hollow fiber membrane adopts solution phase transfer doughnut spinning technique, it is characterized in that described preparation method may further comprise the steps:
(1). polyether sulfone or polysulfones, solvent, pore former are mixed in following ratio:
Polyether sulfone or polysulfones 10～40wt%;
Solvent 50～80wt%;
Pore former 2～40wt%;
Above-mentioned solution stirring and dissolving is even, make the basement membrane spinning solution of composite hollow fiber membrane;
(2). Kynoar or its copolymer or the mixture of the two, solvent, pore former are mixed in following ratio:
Kynoar or its copolymer or the mixture 10～40wt% of the two;
Solvent 50～80wt%;
Pore former 2～40wt%;
Above-mentioned solution stirring and dissolving is even, make the composite bed spinning solution of composite hollow fiber membrane;
(3). above-mentioned two kinds of spinning solutions are extruded simultaneously by the spinning head and the core liquid in the pore of spinning head center of doughnut spinning-drawing machine, enter then in the outer coagulating bath, solvent in two kinds of spinning solutions that make in above-mentioned steps (1), (2) and pore former enter and solidify liquid phase, and as the polymer of composite bed and basal lamina material because phase transfer and precipitating becomes the polymer hollow-fibre membrane, thereby be spun into the composite hollow fiber membrane that comprises composite bed and basement membrane.
2. the preparation method of a kind of composite hollow fiber membrane according to claim 1, it is characterized in that described composite material is the wherein a kind of mixture in a kind of and following polymer in Kynoar and its copolymer: polymethyl methacrylate, polyvinyl alcohol, polyvinyl acetate, polyacrylonitrile, Pioloform, polyvinyl acetal etc., the total content that composite material accounts for the composite bed spinning solution is constant.
3. the preparation method of a kind of composite hollow fiber membrane according to claim 2 is characterized in that described polyvinylidene fluoride alkene copolymer is no less than 60% copolymer for the vinylidene repetitive.
4. the preparation method of a kind of composite hollow fiber membrane according to claim 3 is characterized in that it is intensive polar solvent that the solvent of pore former and polymer is dissolved in used being used in described composite bed spinning solution or the basement membrane spinning solution; Described solvent is the mixture of following one or more solvents: dimethyl formamide, dimethylacetylamide, N-methyl pyrrolidone, triethyl phosphate, sulfolane, dimethyl sulfoxide (DMSO) etc.
5. the preparation method of a kind of composite hollow fiber membrane of stating according to claim 4 is characterized in that described pore former is inorganic pore former or organic polymer pore former or is the two mixture.
6. the preparation method of a kind of composite hollow fiber membrane of stating according to claim 5 is characterized in that described inorganic pore former is following one or more mixture: lithium nitrate, sodium chloride, calcium chloride, calcium carbonate, calcium nitrate, silica, alundum (Al, kaolin.
7. the preparation method of a kind of composite hollow fiber membrane of stating according to claim 6 is characterized in that described organic polymer pore former is following one or more mixture: water soluble polymers such as polyethylene glycol, polyoxyethylene, polyvinylpyrrolidone, polyvinyl alcohol, methylcellulose.
8. according to the preparation method of claim 1 or 2 or 3 or 4 or 5 or 6 or 7 a kind of composite hollow fiber membranes of stating, it is characterized in that also comprising in the described spinning solution surfactant, its content in composite bed or basement membrane spinning solution is 0.01～5wt%, and the content of the pore former in described composite bed spinning solution or the basement membrane spinning solution is 2～39wt% at this moment; Described surfactant is following one or more mixture: cationic surface active agent, anionic surfactant, amphoteric surfactant, nonionic surface active agent.
9. the preparation method of a kind of composite hollow fiber membrane of stating according to Claim 8 is characterized in that also comprising cosolvent in described composite bed spinning solution or the basement membrane spinning solution, and the cosolvent total content in any spinning solution therein is 1～4wt%.
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