CN104667761B - A kind of preparation method of composite hollow fiber membrane - Google Patents
A kind of preparation method of composite hollow fiber membrane Download PDFInfo
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- CN104667761B CN104667761B CN201510085896.2A CN201510085896A CN104667761B CN 104667761 B CN104667761 B CN 104667761B CN 201510085896 A CN201510085896 A CN 201510085896A CN 104667761 B CN104667761 B CN 104667761B
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Abstract
The present invention relates to the preparation method of composite hollow fiber membrane, it is characterised in that comprise the following steps: prepare casting solution；Preparation core liquid and outer coagulation bath；Hollow fiber spinning is to utilize dry and wet spinning equipment that core liquid injects together with casting solution spinning head, and extrudes from spinning head together, prepares hollow fiber film thread；By the hollow fiber film thread of above-mentioned steps gained after the dry-spinning path of 0 35cm, sequentially enter and the first coagulation bath and the second coagulation bath carry out gel phase conversion, form the polymeric hollow fiber multihole film with micropore canals.The composite hollow fiber membrane that the inventive method prepares is hydrophilic hollow membrane material, and it under low pressure has higher membrane flux, and anti-fouling performance is good, simultaneously because the complementarity of raw material makes hollow-fibre membrane have more preferable mechanical strength.
Description
Technical field
The present patent application is on 09 17th, 2013 applying date, Application No.: 201310423328.X, the divisional application of the application for a patent for invention of entitled " preparation method of a kind of composite hollow fiber membrane ".The invention belongs to macromolecule material preparation area, particularly relate to a kind of high intensity, the preparation method of high-throughout composite hollow fiber membrane.
Background technology
Hollow-fibre membrane is mainly used in the filtration in various field or dialysis.Employing composite membrane designs, and can study respectively and separate composite bed membrane material and basal lamina material with selection, it is easy to obtaining the separation film of high separation function, high transmission flux, therefore, composite membrane technology has become an important development direction in high functional membrane technology of preparing.
In the actual application of ultrafilter membrane, a major issue is that fouling membrane causes film permeation flux significantly to be decayed, by charged modification or hydrophilically modified, the resistance tocrocking of membrane material can be improved, but along with modified degree increases, often leading to membrane material strength reduction, especially for hollow-fibre membrane, film-strength is provided by separation membrane material self completely, therefore, it is selected to the high raw material of the mechanical strength of reinforcing membrane prepare hollow-fibre membrane and become the direction of research and development.
Use complex technique can reduce the high score consumption 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 the preparation method of a kind 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 below scheme:
The preparation method of a kind of composite hollow fiber membrane, it is characterised in that comprise the following steps:
Step one: prepare casting solution；It is by macromolecular material, solvent, additive and chemical reaction porogen blended under agitation 12-18h at a temperature of 60-70 DEG C, constant temperature standing and defoaming 20-36h at 60-70 DEG C, obtains homogenizing casting solution；
Step 2: preparation core liquid and outer coagulation bath；Described core liquid consisting of in parts by weight: the dimethyl acetylamide of 40-50 part, the sodium bicarbonate 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；It is to utilize dry-wet spinning equipment that core liquid injects together with casting solution spinning head, and extrudes from spinning head together, prepare 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, sequentially enter and the first coagulation bath and the second coagulation bath carry out gel phase conversion, form the polymeric hollow fiber multihole film with micropore canals；To have the polymeric hollow fiber multihole film of micropore canals soaking and washing in water and obtain to complete split-phase a hollow fiber porous film of even aperture distribution, and be immersed in glycerol containing 35wt% with in the protection liquid of water composition.
Described casting solution is prepared from according to the raw material of following mass percent:
Macromolecular material 13-27%, chemical reaction porogen 6-12%, solvent 60-75%, additive 1-7%.
Described macromolecular material is that cyanethyl cellulose, cellulose xanthate and polyether sulfone are according to the mixture that mass ratio is that 20:20:6-15 makes.
Described chemistry porogen is the mixture that methylcellulose, titanium dioxide, aluminium sesquioxide are made according to mass ratio 5:2:2.
Described solvent is that N-Methyl pyrrolidone and sulfolane are according to the mixture that mass ratio is that 3:1 makes.
Described additive be dodecanamide propyl amine oxide, polymethyl methacrylate, zinc chloride be 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 be mass fraction be the dimethyl sulphoxide solution of 30%, the temperature of described first coagulation bath is 60 DEG C, described second coagulation bath be mass fraction be the dimethyl sulphoxide solution of 25%, the temperature 70 C of described second coagulation bath.
The preparation method of this composite hollow fiber membrane has the advantages that
Polyether sulfone in the present invention is a hydrophobic membrane material of class, and the membrane material of this class has good mechanical property, the feature that initial flux is high, but owing to its hydrophilicity is poor, on the surface of the film, fouling membrane is serious for the substantial amounts of absorption of impurity, flux decline is fast, and film is difficult to clean.And hydrophilic film is in the mass transport process filtered, the polluters such as colloid, oil, protein are agglomerated into spherical on film surface, this spherical agglomerated thing, it is easy to depart from from film surface, just can be cleaned up by simple backwash, hydrophilic ultrafiltration membrane operation pressure is low and Chemical cleaning frequency is low.Cyanethyl cellulose strong for hydrophilic and cellulose xanthate are combined with polyether sulfone by the present invention by composite membrane technology, have prepared good mechanical property, and flux is big, and the hollow-fibre membrane that anti-pollution is easily cleaned again simultaneously, the performance of multiple material is the most complementary.
In the present invention, to have more preferable film connective for dimethyl sulfoxide as coagulation bath, under the temperature conditions of given 60-70 DEG C, concentration be the dimethyl sulfoxide of 25-30% as coagulation bath time the porosity that obtains maximum.
The complex work chemistry porogen that present invention employs inorganic chemistry porogen and organic chemistry porogen can make the hollow-fibre membrane prepared have more preferable pore-forming effect, and aperture is suitable, and porosity is big.
The compound additive that the present invention uses be dodecanamide propyl amine oxide, polymethyl methacrylate, zinc chloride its can preferably improve the surface tension of solution, improve the viscosity of spinning liquid, stand stability and pore-creating character.
The composite membrane that the inventive method prepares is hydrophilic 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 porogen 10%, blended under agitation 12h at a temperature of 60 DEG C, constant temperature standing and defoaming 25h at 60 DEG C, obtains homogenizing casting solution；Macromolecular material is that cyanethyl cellulose, cellulose xanthate and polyether sulfone are according to the mixture that mass ratio is that 20:20:6 makes, solvent is that N-Methyl pyrrolidone and sulfolane are according to the mixture that mass ratio is that 3:1 makes, additive be dodecanamide propyl amine oxide, polymethyl methacrylate, zinc chloride be the mixture that 1:5:3 makes according to mass ratio, chemical reaction porogen is the mixture that methylcellulose, titanium dioxide, aluminium sesquioxide are made according to mass ratio 5:2:2.
Step 2: preparation core liquid and outer coagulation bath；Described core liquid consisting of in parts by weight: the dimethyl acetylamide of 40 parts, the sodium bicarbonate 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 be mass fraction be the dimethyl sulphoxide solution of 30%, the temperature of the first coagulation bath is 60 DEG C, the second coagulation bath be mass fraction be the dimethyl sulphoxide solution of 25%, the temperature 70 C of the second coagulation bath.
Step 3: hollow fiber spinning is to utilize dry-wet spinning equipment that core liquid injects together with casting solution spinning head, and extrudes from spinning head together, prepares 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, sequentially enter and the first coagulation bath and the second coagulation bath carry out gel phase conversion, form the polymeric hollow fiber multihole film with micropore canals；To have the polymeric hollow fiber multihole film of micropore canals soaking and washing in water and obtain to complete split-phase a hollow fiber porous film of even aperture distribution, and be immersed in glycerol containing 35wt% with in the protection liquid of water composition.
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 porogen 8%, blended under agitation 18h at a temperature of 60 DEG C, constant temperature standing and defoaming 36h at 70 DEG C, obtains homogenizing casting solution；Macromolecular material is that cyanethyl cellulose, cellulose xanthate and polyether sulfone are according to the mixture that mass ratio is that 20:20:15 makes, solvent is that N-Methyl pyrrolidone and sulfolane are according to the mixture that mass ratio is that 3:1 makes, additive be dodecanamide propyl amine oxide, polymethyl methacrylate, zinc chloride be the mixture that 1:5:3 makes according to mass ratio, chemical reaction porogen is the mixture that methylcellulose, titanium dioxide, aluminium sesquioxide are made according to mass ratio 5:2:2.
Step 2: preparation core liquid and outer coagulation bath；Described core liquid consisting of in parts by weight: the dimethyl acetylamide of 50 parts, the sodium bicarbonate 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 be mass fraction be the dimethyl sulphoxide solution of 30%, the temperature of the first coagulation bath is 60 DEG C, the second coagulation bath be mass fraction be the dimethyl sulphoxide solution of 25%, the temperature 70 C of the second coagulation bath.
Step 3: hollow fiber spinning is to utilize dry-wet spinning equipment that core liquid injects together with casting solution spinning head, and extrudes from spinning head together, prepares 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, sequentially enter and the first coagulation bath and the second coagulation bath carry out gel phase conversion, form the polymeric hollow fiber multihole film with micropore canals；To have the polymeric hollow fiber multihole film of micropore canals soaking and washing in water and obtain to complete split-phase a hollow fiber porous film of even aperture distribution, and be immersed in glycerol containing 35wt% with in the protection liquid of water composition.
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 porogen 7%, blended under agitation 16h at a temperature of 65 DEG C, constant temperature standing and defoaming 28h at 65 DEG C, obtains homogenizing casting solution；Macromolecular material is that cyanethyl cellulose, cellulose xanthate and polyether sulfone are according to the mixture that mass ratio is that 20:20:10 makes, solvent is that N-Methyl pyrrolidone and sulfolane are according to the mixture that mass ratio is that 3:1 makes, additive be dodecanamide propyl amine oxide, polymethyl methacrylate, zinc chloride be the mixture that 1:5:3 makes according to mass ratio, chemical reaction porogen is the mixture that methylcellulose, titanium dioxide, aluminium sesquioxide are made according to mass ratio 5:2:2.
Step 2: preparation core liquid and outer coagulation bath；Described core liquid consisting of in parts by weight: the dimethyl acetylamide of 45 parts, the sodium bicarbonate 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 be mass fraction be the dimethyl sulphoxide solution of 30%, the temperature of the first coagulation bath is 60 DEG C, the second coagulation bath be mass fraction be the dimethyl sulphoxide solution of 25%, the temperature 70 C of the second coagulation bath.
Step 3: hollow fiber spinning is to utilize dry-wet spinning equipment that core liquid injects together with casting solution spinning head, and extrudes from spinning head together, prepares 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, sequentially enter and the first coagulation bath and the second coagulation bath carry out gel phase conversion, form the polymeric hollow fiber multihole film with micropore canals；To have the polymeric hollow fiber multihole film of micropore canals soaking and washing in water and obtain to complete split-phase a hollow fiber porous film of even aperture distribution, and be immersed in glycerol containing 35wt% with in the protection liquid of water composition.
In the present invention, to have more preferable film connective for dimethyl sulfoxide as coagulation bath, under the temperature conditions of given 60-70 DEG C, concentration be the dimethyl sulfoxide of 25-30% as coagulation bath time the porosity that obtains maximum.The complex work chemistry porogen that present invention employs inorganic chemistry porogen and organic chemistry porogen can make the hollow-fibre membrane prepared have more preferable pore-forming effect, and aperture is suitable, and porosity is big.The product porosity that the present invention prepares is more than 78%.
Cyanethyl cellulose strong for hydrophilic and cellulose xanthate are combined with polyether sulfone by the present invention by composite membrane technology, have prepared good mechanical property, and flux is big, and the hollow-fibre membrane that anti-pollution is easily cleaned again simultaneously, the performance of multiple material is the most complementary.Product of the present invention is at 0.1Mpa, and the pure water flux measured under the conditions of 25 DEG C is 1150-1450L/m2·h；Wall thickness is 0.2-0.5mm, and rupture strength is at more than 0.95Mpa.
Above in conjunction with specific embodiment, the present invention is carried out exemplary description; obviously the realization of the present invention is not subject to the restrictions described above; if the various improvement that the method design that have employed the present invention is carried out with technical scheme; or the most improved design by the present invention and technical scheme directly apply to other occasion, the most within the scope of the present invention.
Claims (1)
1. the preparation method of a composite hollow fiber membrane, it is characterised in that comprise the following steps:
Step one: prepare casting solution；It is by macromolecular material, solvent, additive and chemical reaction porogen blended under agitation 12-18h at a temperature of 60-70 DEG C, constant temperature standing and defoaming 20-36h at 60-70 DEG C, obtains homogenizing casting solution；
Step 2: preparation core liquid and outer coagulation bath；Described core liquid consisting of in parts by weight: the dimethyl acetylamide of 40-50 part, the sodium bicarbonate 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 includes the first coagulation bath and the second coagulation bath；
Step 3: hollow fiber spinning；It is to utilize dry-wet spinning equipment that core liquid injects together with casting solution spinning head, and extrudes from spinning head together, prepare 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, sequentially enter and the first coagulation bath and the second coagulation bath carry out gel phase conversion, form the polymeric hollow fiber multihole film with micropore canals；To have the polymeric hollow fiber multihole film of micropore canals soaking and washing in water and obtain to complete split-phase a hollow fiber porous film of even aperture distribution, and be immersed in glycerol containing 35wt% with in the protection liquid of water composition；Described casting solution is prepared from according to the raw material of following mass percent: macromolecular material 13-27%, chemical reaction porogen 6-12%, solvent 60-75%, additive 1-7%；Described macromolecular material is that cyanethyl cellulose, cellulose sulfonate and polyether sulfone are according to the mixture that mass ratio is that 20:20:6-15 makes；Described chemical reaction porogen is the mixture that methylcellulose, titanium dioxide, aluminium sesquioxide are made according to mass ratio 5:2:2；Described solvent is that N-Methyl pyrrolidone and sulfolane are according to the mixture that mass ratio is that 3:1 makes.
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| CN201510085896.2A CN104667761B (en) | 2013-09-17 | 2013-09-17 | A kind of preparation method of composite hollow fiber membrane |
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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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| CN104667760B (en) * | 2013-09-17 | 2016-08-31 | 殷逢宝 | A kind of preparation method of composite hollow fiber membrane |
| 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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| JP2007245108A (en) * | 2006-03-20 | 2007-09-27 | Daicel Chem Ind Ltd | Hollow fiber porous membrane |
| US8337598B2 (en) * | 2008-09-05 | 2012-12-25 | Honeywell International Inc. | Photo-crosslinked gas selective membranes as part of thin film composite hollow fiber membranes |
| RU2569590C2 (en) * | 2010-03-05 | 2015-11-27 | Сомют Б.В. | Hollow-fibre membrane |
| KR101391653B1 (en) * | 2011-12-30 | 2014-05-07 | 도레이케미칼 주식회사 | Hollow fiber type forward osmosis membrane and manufacturing method thereof |
| CN103212302B (en) * | 2013-04-03 | 2016-01-06 | 北京工业大学 | A kind of chemical reaction induction phase inversion prepares the method for polymeric hollow fiber multihole film |
| CN104667760B (en) * | 2013-09-17 | 2016-08-31 | 殷逢宝 | A kind of preparation method of composite hollow fiber membrane |
| CN104923087B (en) * | 2013-09-17 | 2017-12-29 | 新昌县合控科技有限公司 | A kind of composite hollow fiber membrane |
| CN104689725B (en) * | 2013-09-17 | 2016-08-31 | 殷逢宝 | A kind of preparation method of composite hollow fiber membrane |
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Address after: 541002 No. two, No. 5, West Road, Xiangshan District, Guilin, the Guangxi Zhuang Autonomous Region Patentee after: Yin Fengbao Address before: Jiangdong District 315040 Zhejiang city of Ningbo province was driving road No. 1088 building 001 Patentee before: Yin Fengbao |
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Effective date of registration: 20181225 Address after: 511442 Nancun Town Jiangnan Village Industrial Development Zone, Panyu District, Guangzhou City, Guangdong Province (Complex Building) Patentee after: WATER-CODE MEMBRANE TECHNOLOGY CO.,LTD. Address before: 541002 No. 5 West Road two, Xiangshan District, Guilin, the Guangxi Zhuang Autonomous Region. Patentee before: Yin Fengbao |
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