CN103877869A - Porous membrane made of polytetrafluoroethylene hollow fibers, preparation method and application thereof in membrane contactor - Google Patents
Porous membrane made of polytetrafluoroethylene hollow fibers, preparation method and application thereof in membrane contactor Download PDFInfo
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- CN103877869A CN103877869A CN201210558832.6A CN201210558832A CN103877869A CN 103877869 A CN103877869 A CN 103877869A CN 201210558832 A CN201210558832 A CN 201210558832A CN 103877869 A CN103877869 A CN 103877869A
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Abstract
The invention relates to a porous membrane made of polytetrafluoroethylene hollow fibers, a preparation method and an application thereof in membrane contractor. A silica precursor carries out in-situ reactions in a polytetrafluoroethylene spinning solution to generate silica nano particles, and then a silane coupling agent is added into the solution to evenly disperse the silica nano particles so as to obtain the pore-forming agent used in the film-forming process of hollow fiber membrane. The wires for spinning membranes are subjected to a series of treatments such as proper drying, sintering, stretching, extracting, and washing so as to obtain hydrophobic polytetrafluoroethylene hollow membranes with a certain micro-porous structure. The porous membrane made of polytetrafluoroethylene hollow fibers has a very good application prospect in the field of membrane contactor.
Description
Technical field
The present invention relates to a kind of preparation method of polytetrafluoroethylhollow hollow fiber perforated membrane and the application in membrane contactor thereof.
Background technology
Polytetrafluoroethylene (PTFE) material has outstanding chemical stability, good high and low temperature resistance and good corrosion resistance, and the particulate that the filtering material of therefore preparing with PTFE can be widely used under harsh conditions separates.Meanwhile, due to the strong-hydrophobicity of itself, PTFE also becomes the desirable membrane material of preparing waterproof and breathable, film distillation, osmotic distillation and membrane contactor process.But PTFE is insoluble to common solvent, in the time of high temperature, viscosity is large, poor fluidity, the characteristic of " insoluble not molten " makes its processing characteristics very poor, cannot as the materials such as polysulfones, polypropylene and Kynoar, adopt wet spinning or melt spinning to be prepared into doughnut membrane material.
Manufacturing process as far back as nineteen fifty-three by du pont company's exploitation PTFE fiber, nineteen fifty-seven is realized suitability for industrialized production.But because its structural particularity of PTFE is unsuitable for making fiber by common solwution method and fusion method, although therefore PTFE fiber industryization is produced nearly 50 years, also only have so far fewer companies to produce PTFE fiber product.It is 4 kinds of spinning technique routes of having developed that carrier spinning, pasty state extrusion spinning, melt spinning process, film split spinning technique.Wherein carrier spinning is the main method of industrial production PTFE fiber, is generally PTFE emulsion to be become fibroid carrier be mixed and made into spinning solution with viscose glue or polyvinyl alcohol water solution etc., and spinning solution is squeezed into spinneret and carried out wet spinning after filter.Spinneret be placed on sodium sulphate etc. in coagulating bath, mixed liquor is condensed into fiber in coagulating bath.Shaped fibers at high temperature carries out sintering by carrier carbonization removal through washing with after being dried, then the fiber after sintering is suitably stretched, and fiber gets product.
At present, the report of preparing PTFE hollow fiber porous film by support methods is also less, and its manufacture method is mainly also to improve in the manufacturing process of PTFE fiber.For example, open in JP2012132120-A, the PTFE as-spun fibre of preparing by support methods, after oversintering stretching process, can be used for the production of bag filter.Patent JP2010047859-A utilizes cellulose and derivative thereof to prepare fluorine-containing doughnut as carrier, and unsintered doughnut can be applicable to textile industry.Guo Yuhai, by improving spinning solution formula, develops a kind of preparation method (CN1970847A) of polytetrafluoroethylene fibre of work simplification.The boric acid adding reacts with carrier polyvinyl alcohol as crosslinking agent, has reduced carrier consumption, and contributes to the removal of carrier by oxidant, has obtained umbrinaceous PTFE fiber; The people such as Xiao Changfa disclose a kind of method of manufacturing polytetrafluoroethylporous porous membrane by blend inorganic particulate in spinning solution in patent CN101607178A, its test result shows, the ratio of inorganic micro powder is very remarkable on the impact of water flux, and after stretching, flux increase is more obvious.
Than other preparation methods, support methods is prepared PTFE microporous barrier and conventionally need to be added appropriate pore-foaming agent to obtain high porosity, conventional pore-foaming agent can be divided into the particle (inorganic particulate) of soluble-salt and non-solubility, and comparatively speaking, the pore effect of non-solubility particle is more remarkable.The particle pore-foaming agent of the disclosed non-solubility of present stage patent is all the adding method that adopts blend substantially; because the particle of non-solubility is water insoluble; only depend on mechanical agitation suspended dispersed in spinning solution; therefore conventionally can there is particle aggregation or disperse unequal phenomenon; be unfavorable for spinning and stretch processing, easily cause defect.
Summary of the invention
The technical problem to be solved in the present invention is the reunion of non-solubility particle generation or disperses uneven problem.
For addressing the above problem, the present invention is prepared in carrier spinning on the basis of PTFE microporous barrier, adopts the adding method of original position compound particle, has overcome particle aggregation and has disperseed unequal shortcoming.
Specifically, the invention provides a kind of preparation method of the PTFE hollow fiber porous film for membrane contactor, it is using ptfe emulsion as raw material, adopt polyvinyl alcohol as carrier, in spinning solution, add silica precursor in situ synthetic silica nano particle as the pore-foaming agent in film forming procedure, and adopt silane coupler to make it dispersed, prepare polytetrafluoroethylhollow hollow fiber membrane by solution spinning.The film silk that spins after suitably dry, sintering, stretching, extraction such as wash at the processing, can make the hydrophobicity polytetrafluoroethylhollow hollow fiber membrane with certain microcellular structure.
Adopt said method, by PTFE spinning solution situ generate Nano particles of silicon dioxide as pore-foaming agent, then prepare the PTFE hollow-fibre membrane with certain microcellular structure by the method for carrier spinning, can significantly improve nano particle in conventional physical Blending Processes and disperse phenomenon uneven, that easily reunite, and process is simple, easy to operate, mild condition, need particular instrument, be easy to amplify and commercial Application.
The present invention also provides a kind of membrane contactor being prepared from by polytetrafluoroethylhollow hollow fiber perforated membrane.This hollow fiber membrane contactors can be applicable to natural gas purification, biogas purifying, flue gas treatment, the aspects such as water deoxygenation.
The present invention utilizes silica presoma to be hydrolyzed in PTFE spinning solution and generates well-distributed Nano particles of silicon dioxide, and further improves its dispersiveness in spinning solution by silane coupler.Gained spinning solution evenly, good spinning property, without reuniting or caking phenomenon occurs.The film silk that spins after suitably dry, sintering, stretching, extraction such as wash at the processing, can obtain and there is hydrophobicity PTFE hollow-fibre membrane certain microcellular structure, that be applicable to membrane contactor.
For achieving the above object, the technical solution used in the present invention is:
(1) preparation of PTFE spinning solution: PTFE emulsion and polyvinyl alcohol water solution are evenly mixed, add after the crosslinking agents such as boric acid, obtain spinning solution;
(2) Nano particles of silicon dioxide is synthetic in the original position of spinning solution: in above-mentioned spinning solution, add appropriate silane coupler, add silicon precursor and a small amount of catalyst, reaction certain hour after having reacted;
(3) preparation of nascent PTFE doughnut: spinning solution, after vacuum defoamation, adopts wet spinning to make PTFE as-spun fibre in coagulating bath;
(4) post processing of nascent PTFE doughnut: after drying, the post processing such as carry out that sintering, stretching, extraction are washed is to make the PTFE hollow fiber porous film with certain microcellular structure for nascent PTFE doughnut.
The preparation of described PTFE spinning solution, wherein the mass fraction of PTFE emulsion is that 30-70%, pH value are 8-10, can adopt commercial product or self-control;
The preparation of described PTFE spinning solution, wherein the polyvinyl alcohol degree of polymerization is that 1700-2800, alcoholysis degree are 88-99%, can adopt commercial product, the 5%-20% that its quality is PTFE;
Described Nano particles of silicon dioxide is synthetic in the original position of spinning solution, wherein silane coupler is: VTES, gamma-aminopropyl-triethoxy-silane, γ-glycidoxypropyltrimethoxy silane, gamma-methyl allyl acyloxypropyl trimethoxysilane, γ-mercaptopropyl trimethoxysilane, its addition accounts for the 1%-10% of silica presoma weight, reaction temperature is 20-60 DEG C, and the reaction time is 2-8h;
Described Nano particles of silicon dioxide is synthetic in the original position of spinning solution, and wherein silica presoma is methyl silicate (TMOS) or ethyl orthosilicate (TEOS), and its addition accounts for the 5%-30% of polytetrafluoroethylene (PTFE) weight; Hydrolysising condition is acid catalysis or base catalysis, and catalyst can be ammoniacal liquor, hydrochloric acid or acetic acid etc., and pH value in reaction is 3-11, and reaction temperature is 20-60 DEG C, and the reaction time is 5-30 hour;
The preparation of described nascent PTFE doughnut, wherein spinning solution temperature is 20-50 DEG C; Coagulating bath and core liquid are metabisulfite solution, and pH is 9-13, and temperature is 20-60 DEG C;
The post processing of described nascent PTFE doughnut, wherein drying mode is that nature dries or replaces rear being dried, and sintering temperature is 340-400 DEG C, and sintering time is 1-10min, and draft temperature is 200-300 DEG C, draw ratio is 1-3 times; The NaOH that extraction washing lotion is 5-20% or the aqueous solution of potassium hydroxide, the extraction time of washing is 24-72h.The porosity of gained PTFE hollow fiber porous film is 20-60%, and average pore size is 0.05-2.0 μ m, and contact angle is 100-120 °.
The film silk prepared according to said method is applicable to being prepared into hollow fiber membrane contactors, is applied to the aspects such as natural gas purification, biogas purifying, flue gas treatment, water deoxygenation.
Detailed description of the invention
Below in conjunction with embodiment in detail the present invention is described in detail.
Embodiment 1
100g PVA1788 is dissolved in 400g water, after dissolving completely, adds PTFE emulsion (60wt%) 1660g, after stirring, add successively again silane coupler 10g gamma-aminopropyl-triethoxy-silane, 100g ethyl orthosilicate, the about 4h of mechanical agitation under normal temperature, after vacuum defoamation, wet spinning.Gained as-spun fibre is after the operations such as natural drying, sintering, stretching are processed, then in 5% sodium hydrate aqueous solution, extraction is washed 48h, obtains PTFE hollow fiber porous film.Sintering condition: 380 DEG C, 5min, draft temperature: 300 DEG C, draw ratio: 1.5 times.Gained film silk porosity is 30%, and average pore size is 0.2 μ m, and contact angle is 105 °.PTFE hollow fiber porous film silk is processed into membrane contactor assembly, with 15% CO
2/ N
2gaseous mixture is that the diethanol amine aqueous solution of unstripped gas, mass fraction 30% is absorbent, test CO
2removal effect.In the time that operating pressure is 1.0MPa, CO
2removal efficiency reaches 76%.
Embodiment 2
100gPVA2488 is dissolved in 400g water, after dissolving completely, adds PTFE emulsion (60wt%) 1660g, after stirring, add successively again silane coupler 20g gamma-aminopropyl-triethoxy-silane, 200g ethyl orthosilicate, the about 8h of mechanical agitation under normal temperature, after vacuum defoamation, wet spinning.Gained as-spun fibre is after the operations such as natural drying, sintering, stretching are processed, then in 20% sodium hydrate aqueous solution, extraction is washed 48h, obtains PTFE hollow fiber porous film.Sintering condition: 380 DEG C, 5min, draft temperature: 300 DEG C, draw ratio: 1.5 times, gained film silk porosity is 42%, and average pore size is 0.7 μ m, and contact angle is 115 °.PTFE hollow fiber porous film silk is processed into membrane contactor assembly, with 15% CO
2/ N
2gaseous mixture is that the diethanol amine aqueous solution of unstripped gas, mass fraction 30% is absorbent, test CO
2removal effect.In the time that operating pressure is 1.0MPa, CO
2removal efficiency reaches 87%.
Embodiment 3
100gPVA1799 is dissolved in 400g water, after dissolving completely, add PTFE emulsion (60wt%) 1660g, after stirring, add successively again silane coupler 10g γ-glycidoxypropyltrimethoxy silane, 100g methyl silicate, the about 8h of mechanical agitation under normal temperature, after vacuum defoamation, wet spinning.Gained as-spun fibre is after the operations such as natural drying, sintering, stretching are processed, then in 20% sodium hydrate aqueous solution, extraction is washed 48h, obtains PTFE hollow fiber porous film.Sintering condition: 360 DEG C, 8min, draft temperature: 300 DEG C, draw ratio: 2 times, gained film silk porosity is 48%, and average pore size is 1.0 μ m, and contact angle is 108 °.PTFE hollow fiber porous film silk is processed into membrane contactor assembly, with 15% CO
2/ N
2gaseous mixture is that the diethanol amine aqueous solution of unstripped gas, mass fraction 30% is absorbent, test CO
2removal effect.In the time that operating pressure is 1.0MPa, CO
2removal efficiency reaches 90%.
Tool of the present invention has the following advantages: the gentle easily control of reaction condition, and easy to operate and safe, equipment, without particular/special requirement, is more easily realized serialization and produced.The method of the synthetic pore-foaming agent of original position can be dispersed in spinning solution Nano particles of silicon dioxide, overcome that pore-foaming agent in blending method is easily reunited, the shortcoming of caking, skewness.PTFE hollow-fibre membrane prepared by the method has uniform microcellular structure, good mechanical performance and chemical stability, and has kept the strong-hydrophobicity of PTFE material itself, has good application prospect in membrane contactor field.
Claims (10)
1. a preparation method for polytetrafluoroethylhollow hollow fiber perforated membrane, is characterized in that:
Using ptfe emulsion as raw material, adopt polyvinyl alcohol as carrier, in spinning solution, add silica precursor in situ synthetic silica nano particle as the pore-foaming agent in film forming procedure, and adopt silane coupler to make it dispersed, prepare polytetrafluoroethylhollow hollow fiber membrane by solution spinning;
The polytetrafluoroethylhollow hollow fiber membrane silk that spins make the hydrophobicity polytetrafluoroethylhollow hollow fiber membrane with microcellular structure through suitable post processing.
2. a preparation method for polytetrafluoroethylhollow hollow fiber perforated membrane described in claim 1, is characterized in that:
Using ptfe emulsion as raw material, adopt polyvinyl alcohol as carrier, in spinning solution, add silica precursor in situ synthetic silica nano particle as the pore-foaming agent in film forming procedure, and adopt silane coupler to make it dispersed, prepare polytetrafluoroethylhollow hollow fiber membrane by solution spinning;
The polytetrafluoroethylhollow hollow fiber membrane silk that spins make the hydrophobicity polytetrafluoroethylhollow hollow fiber membrane with microcellular structure through suitable post processing.
3. according to the preparation method of polytetrafluoroethylhollow hollow fiber perforated membrane described in claim 2, it is characterized in that:
The mass fraction of ptfe emulsion used is that 30-70%, pH value are 8-10;
The polyvinyl alcohol degree of polymerization used is that 1700-2800, alcoholysis degree are 88-99%, and its quality is the 5%-20% of PTFE quality.
4. according to polytetrafluoroethylhollow hollow fiber method for preparing porous film claimed in claim 2, it is characterized in that: silica presoma is methyl silicate (TMOS) or ethyl orthosilicate (TEOS);
The addition of silica presoma accounts for the 5%-30% of polytetrafluoroethylene (PTFE) quality.
5. according to polytetrafluoroethylhollow hollow fiber method for preparing porous film claimed in claim 2, it is characterized in that: for the silane coupler that improves silica dispersiveness be: VTES, gamma-aminopropyl-triethoxy-silane, γ-glycidoxypropyltrimethoxy silane, gamma-methyl allyl acyloxypropyl trimethoxysilane or γ-mercaptopropyl trimethoxysilane; The addition of silane coupler accounts for the 1%-10% of silica presoma quality.
6. according to the polytetrafluoroethylhollow hollow fiber method for preparing porous film described in claim 2 or 4, it is characterized in that: the hydrolysising condition of silica presoma is acid catalysis or base catalysis, and catalyst can be ammoniacal liquor, hydrochloric acid or acetic acid;
The pH value of original position synthetic silica nano particle reaction is 3-11, and reaction temperature is 20-60 DEG C, and the reaction time is 5-30 hour.
7. according to polytetrafluoroethylhollow hollow fiber method for preparing porous film claimed in claim 2, it is characterized in that:
Post processing refers to that spun polytetrafluoroethylhollow hollow fiber membrane silk drying, sintering, stretching, extraction wash;
The film silk drying mode that spins be nature dry or solvent exchange after dry, the displacement solvent that adopts is ethanol or n-hexane; Sintering temperature is 340-400 DEG C, and sintering time is 1-10min, and draft temperature is 200-300 DEG C, and draw ratio is 1-3 times, and extraction washing lotion is the NaOH of mass concentration 5-20% or the aqueous solution of potassium hydroxide, and the extraction time of washing is 24-72h.
8. according to polytetrafluoroethylhollow hollow fiber method for preparing porous film claimed in claim 2, it is characterized in that: the porosity of polytetrafluoroethylhollow hollow fiber perforated membrane is 20-60%, average pore size is 0.05-2.0 μ m, and contact angle is 100-120 °.
9. the application of polytetrafluoroethylhollow hollow fiber perforated membrane described in a claim 1, it makes membrane contactor as membrane contactor assembly, and membrane contactor assembly is mainly made up of polytetrafluoroethylhollow hollow fiber membrane described in contactor housing, epoxy sealing head, claim 1.
10. according to application claimed in claim 9, it is characterized in that: this polytetrafluoroethylhollow hollow fiber membrane contactor can be used for film absorption process and removes in mist minimum gas in acid ingredient or water; Contactor is an airtight cavity, contactor housing is provided with provides the import of two-phase flow body and outlet, two above polytetrafluoroethylhollow hollow fiber membranes are filled in contactor housing cavity, the two ends of two above polytetrafluoroethylhollow hollow fiber membranes see through respectively the outside that contactor housing stretches out contactor, and two above polytetrafluoroethylhollow hollow fiber membranes are connected with contactor housing seal by epoxy sealing head.
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Cited By (5)
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| CN104524988A (en) * | 2015-01-22 | 2015-04-22 | 联合环境技术（厦门）有限公司 | Polyvinylidene fluoride hollow fiber membrane of in-situ pore-forming agent and preparation method of polyvinylidene fluoride hollow fiber membrane |
| WO2017080456A1 (en) * | 2015-11-11 | 2017-05-18 | 重庆润泽医药有限公司 | Polytetrafluoroethylene ultrafine hollow fiber membrane |
| CN108144456A (en) * | 2016-12-02 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of preparation of polytetrafluoroethylhollow hollow fiber membrane and film and membrane contactor and application |
| CN111077292A (en) * | 2019-12-23 | 2020-04-28 | 上海微谱化工技术服务有限公司 | Pretreatment method for analysis of artificial leather material for vehicle |
| CN112575448A (en) * | 2020-12-11 | 2021-03-30 | 浙江理工大学 | Preparation method of porous non-woven fabric with antibacterial function |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104524988A (en) * | 2015-01-22 | 2015-04-22 | 联合环境技术（厦门）有限公司 | Polyvinylidene fluoride hollow fiber membrane of in-situ pore-forming agent and preparation method of polyvinylidene fluoride hollow fiber membrane |
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| CN108144456A (en) * | 2016-12-02 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of preparation of polytetrafluoroethylhollow hollow fiber membrane and film and membrane contactor and application |
| CN111077292A (en) * | 2019-12-23 | 2020-04-28 | 上海微谱化工技术服务有限公司 | Pretreatment method for analysis of artificial leather material for vehicle |
| CN112575448A (en) * | 2020-12-11 | 2021-03-30 | 浙江理工大学 | Preparation method of porous non-woven fabric with antibacterial function |
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Application publication date: 20140625 |