CN104667761A - Preparation method of composite hollow fiber membrane - Google Patents
Preparation method of composite hollow fiber membrane Download PDFInfo
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- CN104667761A CN104667761A CN201510085896.2A CN201510085896A CN104667761A CN 104667761 A CN104667761 A CN 104667761A CN 201510085896 A CN201510085896 A CN 201510085896A CN 104667761 A CN104667761 A CN 104667761A
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Abstract
The invention relates to a preparation method of a composite hollow fiber membrane. The preparation method is characterized by comprising the following steps: preparing a casting membrane solution; preparing a core solution and an external gel bath; spinning hollow fibers: injecting the core solution and the casting membrane solution into spinning nozzles together by utilizing dry-wet spinning equipment and extruding the core solution and the casting membrane solution from the spinning nozzles together to prepare hollow fiber membrane silk; and after the hollow fiber membrane silk obtained in the above step passes through a 0-35cm dry spinning path, enabling the hollow fiber membrane silk to enter a first gel bath and a second gel bath to undergo gel phase conversion, thus forming the polymer hollow fiber porous membrane with microchannels. The composite hollow fiber membrane prepared by the method is a hydrophilic hollow membrane material, has higher membrane flux under low pressure, has good pollution resistance and also has better mechanical strength due to the complementarity of the raw materials.
Description
Technical field
The present patent application is on 09 17th, 2013 applying date, and application number is: 201310423328.X, the divisional application of the application for a patent for invention that name is called " a kind of preparation method of composite hollow fiber membrane ".The invention belongs to macromolecule material preparation area, particularly relate to the preparation method of a kind of high strength, high-throughout composite hollow fiber membrane.
Background technology
Hollow-fibre membrane is mainly used in filtration in various field or dialysis.Employing composite membrane designs, and can study respectively and be separated composite bed membrane material and basal lamina material with selection, be easy to the diffusion barrier obtaining high separation function, high transmission flux, therefore, composite membrane technology has become an important development direction in high functional membrane technology of preparing.
In milipore filter practical application, a major issue is that fouling membrane causes membrane permeate flux significantly to be decayed, by charged modification or hydrophilically modified, the resistance tocrocking of membrane material can be improved, but along with modification degree increases, often cause membrane material remitted its fury, especially for hollow-fibre membrane, film-strength provided by separation membrane material self completely, therefore, the raw material that can strengthen the mechanical strength of film high are selected to prepare the direction that hollow-fibre membrane becomes research and development.
Adopt complex technique can reduce the consumption of high score from function modified membrane material, introduce complex technique, make hollow fiber separating film higher function, also can reduce membrane material cost.
Summary of the invention
The present invention devises a kind of preparation method of composite hollow fiber membrane, which solves current hollow-fibre membrane mechanical strength low, anti-pollution ability, the problem that flux is little.
In order to solve the technical problem of above-mentioned existence, present invention employs following scheme:
A preparation method for composite hollow fiber membrane, is characterized in that, comprises the following steps:
Step one: prepare casting solution; That constant temperature standing and defoaming 20-36h at 60-70 DEG C, obtains homogeneous casting solution by macromolecular material, solvent, additive and chemical reaction pore-foaming agent blended under agitation 12-18h at the temperature of 60-70 DEG C;
Step 2: preparation core liquid and outer coagulation bath; Described core liquid consisting of according to weight parts: the dimethylacetylamide of 40-50 part, the sodium acid carbonate of 1-5 part, the amylalcohol of 10-15 part, the water of 20-40 part, described core flow quantity 8-10ml/min, described core liquid temp is 40-50 DEG C;
Step 3: hollow fiber spinning; Be utilize dry-wet spinning equipment that core liquid is injected spinning head together with casting solution, and extrude from spinning head together, obtained hollow fiber film thread;
Step 4: prepare hollow-fibre membrane; By the hollow fiber film thread of step 3 gained after the dry-spinning path of 0-35cm, enter successively in the first coagulation bath and the second coagulation bath and carry out gel phase conversion, form the polymeric hollow fiber multihole film with micropore canals; Soaking and washing to the complete phase-splitting in water of the polymeric hollow fiber multihole film with micropore canals is obtained the hollow fiber porous film of even aperture distribution, and in the protection liquid that forms of the glycerine be immersed in containing 35wt% and water.
Described casting solution is prepared from according to the raw material of following mass percent:
Macromolecular material 13-27%, chemical reaction pore-foaming agent 6-12%, solvent 60-75%, additive 1-7%.
Described macromolecular material is cyanethyl cellulose, cellulose xanthate and polyether sulfone is the mixture that 20:20:6-15 makes according to mass ratio.
The mixture that described chemical pore-foaming agent is methylcellulose, titanium dioxide, alundum (Al2O3) are made according to mass ratio 5:2:2.
Described solvent is 1-METHYLPYRROLIDONE and sulfolane is the mixture that 3:1 makes according to mass ratio.
Described additive is dodecanamide propyl amine oxide, polymethyl methacrylate, zinc chloride are the mixture that 1:5:3 makes according to mass ratio.
Spinning speed in step 3 is 12-15m/min.
First coagulation bath described in step 4 to be mass fraction be 30% dimethyl sulphoxide solution, the temperature of described first coagulation bath is 60 DEG C, described second coagulation bath to be mass fraction be 25% dimethyl sulphoxide solution, the temperature 70 C of described second coagulation bath.
The preparation method of this composite hollow fiber membrane has following beneficial effect:
Polyether sulfone in the present invention is the hydrophobic membrane material of a class, and the membrane material of this class has good mechanical property, the feature that initial flux is high, but because its hydrophilicity is poor, on the surface of the film, fouling membrane is serious for a large amount of absorption of impurity, flux decline is fast, and film is difficult to cleaning.And hydrophilic film is in the mass transport process of filtering, the polluters such as colloid, oil, protein are agglomerated into spherical on film surface, this spherical agglomerated thing, are easy to depart from from film surface, just can be cleaned up by simple backwash, hydrophilic ultrafiltration membrane operating pressure is low and Chemical cleaning frequency is low.Cyanethyl cellulose strong for hydrophily and cellulose xanthate are combined with polyether sulfone by composite membrane technology by the present invention, prepare good mechanical property, flux is large, simultaneously the hollow-fibre membrane that easily cleans of anti-pollution again, and the performance of multiple material is just complementary.
Have better film as the dimethyl sulfoxide (DMSO) of coagulation bath in the present invention connective, under the temperature conditions of given 60-70 DEG C, concentration is that the dimethyl sulfoxide (DMSO) of 25-30% is maximum as the porosity obtained during coagulation bath.
The compound that present invention employs inorganic chemistry pore-foaming agent and organic chemistry pore-foaming agent makes chemical pore-foaming agent can make the hollow-fibre membrane obtained have better pore-forming effect, and aperture is suitable, and porosity is large.
The compound additive that the present invention adopts is dodecanamide propyl amine oxide, polymethyl methacrylate, zinc chloride its can better improve the surface tension of solution, improve the viscosity of spinning solution, leave standstill stability and pore-creating character.
The composite membrane that the inventive method obtains is hydrophily hollow membrane material, and it under low pressure has higher membrane flux, and anti-fouling performance is good.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described:
Embodiment 1
The preparation method of composite hollow fiber membrane, comprises the following steps:
Step one: preparing casting solution is by macromolecular material 13%, solvent 75%, additive 2% and chemical reaction pore-foaming agent 10%, blended under agitation 12h at the temperature of 60 DEG C, and constant temperature standing and defoaming 25h at 60 DEG C, obtains homogeneous casting solution; Macromolecular material is cyanethyl cellulose, cellulose xanthate and polyether sulfone is the mixture that 20:20:6 makes according to mass ratio, solvent is 1-METHYLPYRROLIDONE and sulfolane is the mixture that 3:1 makes according to mass ratio, additive is dodecanamide propyl amine oxide, polymethyl methacrylate, zinc chloride are the mixture that 1:5:3 makes according to mass ratio, the mixture that chemical reaction pore-foaming agent is methylcellulose, titanium dioxide, alundum (Al2O3) are made according to mass ratio 5:2:2.
Step 2: preparation core liquid and outer coagulation bath; Described core liquid consisting of according to weight parts: the dimethylacetylamide of 40 parts, the sodium acid carbonate of 1 part, the amylalcohol of 10 parts, the water of 20 parts, core flow quantity 8ml/min, core liquid temp is 40 DEG C; First coagulation bath to be mass fraction be 30% dimethyl sulphoxide solution, the temperature of the first coagulation bath is 60 DEG C, the second coagulation bath to be mass fraction be 25% dimethyl sulphoxide solution, the temperature 70 C of the second coagulation bath.
Step 3: hollow fiber spinning utilizes dry-wet spinning equipment that core liquid is injected spinning head together with casting solution, and extrude from spinning head together, obtained hollow fiber film thread, and spinning speed is 12m/min;
Step 4: prepare hollow-fibre membrane; By the hollow fiber film thread of step 3 gained after the dry-spinning path of 0-35cm, enter successively in the first coagulation bath and the second coagulation bath and carry out gel phase conversion, form the polymeric hollow fiber multihole film with micropore canals; Soaking and washing to the complete phase-splitting in water of the polymeric hollow fiber multihole film with micropore canals is obtained the hollow fiber porous film of even aperture distribution, and in the protection liquid that forms of the glycerine be immersed in containing 35wt% and water.
Embodiment 2
The preparation method of composite hollow fiber membrane, comprises the following steps:
Step one: preparing casting solution is by macromolecular material 27%, solvent 60%, additive 5% and chemical reaction pore-foaming agent 8%, blended under agitation 18h at the temperature of 60 DEG C, and constant temperature standing and defoaming 36h at 70 DEG C, obtains homogeneous casting solution; Macromolecular material is cyanethyl cellulose, cellulose xanthate and polyether sulfone is the mixture that 20:20:15 makes according to mass ratio, solvent is 1-METHYLPYRROLIDONE and sulfolane is the mixture that 3:1 makes according to mass ratio, additive is dodecanamide propyl amine oxide, polymethyl methacrylate, zinc chloride are the mixture that 1:5:3 makes according to mass ratio, the mixture that chemical reaction pore-foaming agent is methylcellulose, titanium dioxide, alundum (Al2O3) are made according to mass ratio 5:2:2.
Step 2: preparation core liquid and outer coagulation bath; Described core liquid consisting of according to weight parts: the dimethylacetylamide of 50 parts, the sodium acid carbonate of 5 parts, the amylalcohol of 15 parts, the water of 40 parts, core flow quantity 10ml/min, core liquid temp is 50 DEG C; First coagulation bath to be mass fraction be 30% dimethyl sulphoxide solution, the temperature of the first coagulation bath is 60 DEG C, the second coagulation bath to be mass fraction be 25% dimethyl sulphoxide solution, the temperature 70 C of the second coagulation bath.
Step 3: hollow fiber spinning utilizes dry-wet spinning equipment that core liquid is injected spinning head together with casting solution, and extrude from spinning head together, obtained hollow fiber film thread, and spinning speed is 15m/min;
Step 4: prepare hollow-fibre membrane; By the hollow fiber film thread of step 3 gained after the dry-spinning path of 0-35cm, enter successively in the first coagulation bath and the second coagulation bath and carry out gel phase conversion, form the polymeric hollow fiber multihole film with micropore canals; Soaking and washing to the complete phase-splitting in water of the polymeric hollow fiber multihole film with micropore canals is obtained the hollow fiber porous film of even aperture distribution, and in the protection liquid that forms of the glycerine be immersed in containing 35wt% and water.
Embodiment 3
The preparation method of composite hollow fiber membrane, comprises the following steps:
Step one: preparing casting solution is by macromolecular material 18%, solvent 68%, additive 7% and chemical reaction pore-foaming agent 7%, blended under agitation 16h at the temperature of 65 DEG C, and constant temperature standing and defoaming 28h at 65 DEG C, obtains homogeneous casting solution; Macromolecular material is cyanethyl cellulose, cellulose xanthate and polyether sulfone is the mixture that 20:20:10 makes according to mass ratio, solvent is 1-METHYLPYRROLIDONE and sulfolane is the mixture that 3:1 makes according to mass ratio, additive is dodecanamide propyl amine oxide, polymethyl methacrylate, zinc chloride are the mixture that 1:5:3 makes according to mass ratio, the mixture that chemical reaction pore-foaming agent is methylcellulose, titanium dioxide, alundum (Al2O3) are made according to mass ratio 5:2:2.
Step 2: preparation core liquid and outer coagulation bath; Described core liquid consisting of according to weight parts: the dimethylacetylamide of 45 parts, the sodium acid carbonate of 3 parts, the amylalcohol of 12 parts, the water of 30 parts, core flow quantity 9ml/min, core liquid temp is 45 DEG C; First coagulation bath to be mass fraction be 30% dimethyl sulphoxide solution, the temperature of the first coagulation bath is 60 DEG C, the second coagulation bath to be mass fraction be 25% dimethyl sulphoxide solution, the temperature 70 C of the second coagulation bath.
Step 3: hollow fiber spinning utilizes dry-wet spinning equipment that core liquid is injected spinning head together with casting solution, and extrude from spinning head together, obtained hollow fiber film thread, and spinning speed is 13m/min;
Step 4: prepare hollow-fibre membrane; By the hollow fiber film thread of step 3 gained after the dry-spinning path of 0-35cm, enter successively in the first coagulation bath and the second coagulation bath and carry out gel phase conversion, form the polymeric hollow fiber multihole film with micropore canals; Soaking and washing to the complete phase-splitting in water of the polymeric hollow fiber multihole film with micropore canals is obtained the hollow fiber porous film of even aperture distribution, and in the protection liquid that forms of the glycerine be immersed in containing 35wt% and water.
Have better film as the dimethyl sulfoxide (DMSO) of coagulation bath in the present invention connective, under the temperature conditions of given 60-70 DEG C, concentration is that the dimethyl sulfoxide (DMSO) of 25-30% is maximum as the porosity obtained during coagulation bath.The compound that present invention employs inorganic chemistry pore-foaming agent and organic chemistry pore-foaming agent makes chemical pore-foaming agent can make the hollow-fibre membrane obtained have better pore-forming effect, and aperture is suitable, and porosity is large.The product porosity that the present invention obtains is more than 78%.
Cyanethyl cellulose strong for hydrophily and cellulose xanthate are combined with polyether sulfone by composite membrane technology by the present invention, prepare good mechanical property, flux is large, simultaneously the hollow-fibre membrane that easily cleans of anti-pollution again, and the performance of multiple material is just complementary.Product of the present invention is at 0.1Mpa, and the pure water flux measured under 25 DEG C of conditions is 1150-1450L/m
2h; Wall thickness is 0.2-0.5mm, and rupture strength is at more than 0.95Mpa.
Above in conjunction with specific embodiments to invention has been exemplary description; obvious realization of the present invention is not subject to the restrictions described above; as long as have employed the various improvement that method of the present invention is conceived and technical scheme is carried out; or design of the present invention and technical scheme directly applied to other occasion, all in protection scope of the present invention without to improve.
Claims (4)
1. a preparation method for composite hollow fiber membrane, is characterized in that, comprises the following steps:
Step one: prepare casting solution; That constant temperature standing and defoaming 20-36h at 60-70 DEG C, obtains homogeneous casting solution by macromolecular material, solvent, additive and chemical reaction pore-foaming agent blended under agitation 12-18h at the temperature of 60-70 DEG C;
Step 2: preparation core liquid and outer coagulation bath; Described core liquid consisting of according to weight parts: the dimethylacetylamide of 40-50 part, the sodium acid carbonate of 1-5 part, the amylalcohol of 10-15 part, the water of 20-40 part, described core flow quantity 8-10ml/min, described core liquid temp is 40-50 DEG C; Outer coagulation bath comprises the first coagulation bath and the second coagulation bath;
Step 3: hollow fiber spinning; Be utilize dry-wet spinning equipment that core liquid is injected spinning head together with casting solution, and extrude from spinning head together, obtained hollow fiber film thread;
Step 4: prepare hollow-fibre membrane; By the hollow fiber film thread of step 3 gained after the dry-spinning path of 0-35cm, enter successively in the first coagulation bath and the second coagulation bath and carry out gel phase conversion, form the polymeric hollow fiber multihole film with micropore canals; Soaking and washing to the complete phase-splitting in water of the polymeric hollow fiber multihole film with micropore canals is obtained the hollow fiber porous film of even aperture distribution, and in the protection liquid that forms of the glycerine be immersed in containing 35wt% and water; Described casting solution is prepared from according to the raw material of following mass percent: macromolecular material 13-27%, chemical reaction pore-foaming agent 6-12%, solvent 60-75%, additive 1-7%; The macromolecular material stated is cyanethyl cellulose, cellulose xanthate and polyether sulfone is the mixture that 20:20:6-15 makes according to mass ratio; The mixture that described chemical pore-foaming agent is methylcellulose, titanium dioxide, alundum (Al2O3) are made according to mass ratio 5:2:2; Described solvent is 1-METHYLPYRROLIDONE and sulfolane is the mixture that 3:1 makes according to mass ratio.
2. the preparation method of composite hollow fiber membrane according to claim 1, is characterized in that: described additive is dodecanamide propyl amine oxide, polymethyl methacrylate, zinc chloride are the mixture that 1:5:3 makes according to mass ratio.
3. the preparation method of composite hollow fiber membrane according to claim 1 and 2, is characterized in that: the spinning speed in step 3 is 12-15m/min.
4. the composite hollow fiber membrane according to claim 1,2 or 3, it is characterized in that: the first coagulation bath described in step 4 to be mass fraction be 30% dimethyl sulphoxide solution, the temperature of described first coagulation bath is 60 DEG C, described second coagulation bath to be mass fraction be 25% dimethyl sulphoxide solution, the temperature 70 C of described second coagulation bath.
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| CN201310423328.XA CN103464002B (en) | 2013-09-17 | 2013-09-17 | Preparation method of composite hollow fiber membrane |
| CN201510085896.2A CN104667761B (en) | 2013-09-17 | 2013-09-17 | A kind of preparation method of composite hollow fiber membrane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104667760A (en) * | 2013-09-17 | 2015-06-03 | 殷逢宝 | Preparation method of composite hollow fiber membrane |
| CN106474942A (en) * | 2015-08-28 | 2017-03-08 | 中国石油化工股份有限公司 | The preparation method of hollow fiber ultrafiltration membrane |
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| CN106474942B (en) * | 2015-08-28 | 2019-04-19 | 中国石油化工股份有限公司 | The preparation method of hollow fiber ultrafiltration membrane |
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