CN102357346B - Polyvinylidene fluoride hollow fiber membrane, preparation method and application - Google Patents
Polyvinylidene fluoride hollow fiber membrane, preparation method and application Download PDFInfo
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- CN102357346B CN102357346B CN2011103480331A CN201110348033A CN102357346B CN 102357346 B CN102357346 B CN 102357346B CN 2011103480331 A CN2011103480331 A CN 2011103480331A CN 201110348033 A CN201110348033 A CN 201110348033A CN 102357346 B CN102357346 B CN 102357346B
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Abstract
The invention discloses a polyvinylidene fluoride hollow fiber membrane used for purification of municipal water, a preparation method, and an application in purification of municipal water; the cross section of the polyvinylidene fluoride hollow fiber membrane shows a spongy structure with mutually crosslinked meshes, and the mesh has an equivalent diameter of 0.1-1 microns.
Description
Technical field
The application that the present invention relates to a kind of polyvinylidene fluoride hollow fiber membrane for the urban water purification, its preparation method and at urban water, purify.
Technical background
Membrane technology as separating, concentrated, purification and purification techniques, developed in recent decades the new and high technology that becomes industrialization rapidly.The advantages such as membrane separation technique is easy to operate owing to having, facility compact, working environment safety, energy savings and chemical reagent, be used widely in the fields such as desalinization, electronics industry, food industry, medical industry, environmental protection and bioengineering and scientific research.Polyvinylidene fluoride (PVDF) is the crystalline white powder half crystalline form polymer of a kind of wire, have that serviceability temperature is high, mechanical performance is good, the series of advantages such as good weatherability, solvent resistance are strong, also have simultaneously outstanding anti-aging characteristic and uvioresistant ability, and easily casting film-forming, be a kind of good material of preparing that development in recent years is got up.
About the preparation method of PVDF separation membrane material, what at present both at home and abroad institute widely applied is non-solvent phase partition method (NIPS), and many documents and patent have relevant report.For the non-solvent phase separation method, Zuo etc. are at Journal of Functional Polymers, and 2008,21(4): introduced in 380-384 and utilized the non-solvent phase separation method by adopting DMAC to be the PVDF milipore filter of finger-like pore structure for solvent obtains inside; EP1009517 adopts the non-solvent phase separation method to make hydrophily or the hydrophobicity asymmetry polyvinylidene fluoride microporous film of high porosity.The common pore-size distribution of the microporous barrier that the non-solvent phase separation method prepares is irregular, and presents the finger-like macroporous structure more,, although this structure can make film forming have higher flux, also can reduce mechanical strength and the separation accuracy of film forming accordingly.
Summary of the invention
For overcoming the above-mentioned defect of the prepared polyvinylidene fluoride separation membrane material of existing non-solvent phase separation method, the present invention, take the mechanism that is separated as basis, works out a kind of can preparing and has high strength, high flux and the high score new method from the polyvinylidene fluoride hollow fiber membrane of precision.
Therefore, one of purpose of the present invention is to provide a kind of polyvinylidene fluoride hollow fiber membrane that urban water purifies that can be used for.
Another object of the present invention is to provide a kind of method for preparing polyvinylidene fluoride hollow fiber membrane.
A further object of the present invention is to provide the application of above-mentioned polyvinylidene fluoride hollow fiber membrane in urban water purifies.
For achieving the above object, the present invention adopts following technical scheme:
A kind of polyvinylidene fluoride hollow fiber membrane for the urban water purification, its cross section is rendered as the spongelike structure that mesh is cross-linked with each other, and the equivalent diameter of mesh is 0.1 ~ 1 μ m.
A kind of method for preparing above-mentioned polyvinylidene fluoride hollow fiber membrane, comprise PVDF powder and two kinds of organic liquid blend, the blend of gained is heated blend at the temperature lower than 50 ~ 90 ℃ of polymer powders fusing points, and by the die head of different pore size size, extrude the doughnut form of making, put into again specific organic solvent and soak in order to extract above-mentioned two kinds of organic liquids, clean and protect again hole agent processing by pure water and obtain finished film after certain hour.
Particularly, polyvinylidene fluoride hollow fiber membrane preparation method of the present invention comprises the steps:
(1) preparation casting solution
Mass percent in the casting solution total amount, polyvinylidene fluoride (powder with 15% ~ 45%, η=1.8 ~ 2.2), 5.5% ~ 76.5% diluent one and 5.5% ~ 76.5% diluent two are put into intermingling apparatus, wherein solid matter carries out drying in advance to remove moisture, and 80 ~ 120 ℃ of lower agitating heating blend, mixing speed is 70 ~ 90r/min with mixture, the blend time is 2-24 hour, preferred 4-16 hour, more preferably 6-12 hour, obtain casting solution;
(2) the spray silk forms doughnut
With above-mentioned casting solution through 4-24 hour, preferred 6-16 hour, after more preferably the vacuum defoamation of 8-12 hour is processed, adding to depress at nitrogen makes casting solution form doughnut through spray silk die head, then the hollow-fibre membrane that will come into being is put into successively extractant and was processed 5 ~ 48 hours, preferred 8-36 hour, more preferably 10-24 hour, cleaning and dipping 5 ~ 48 hours in pure water again, preferred 6-36 hour, more preferably 8-24 hour, and with protecting the hole agent, process 4-24 hour, preferred 6-18 hour, more preferably 8-12 hour, can obtain the hollow-fibre membrane finished product.
The structure of polyvinylidene fluoride hollow fiber membrane of the present invention both can make film have higher water flux, can make again film have higher-strength and than high score from precision, be applicable to urban water fully and purify.
Description of drawings
Fig. 1 is the hollow-fibre membrane flow sheet in one embodiment of the present invention.
Fig. 2 is the cross section ESEM enlarged drawing in one embodiment of the present invention.Wherein, figure (b) is the enlarged drawing of figure (a).
Fig. 3 is the doughnut film sewage treatment system flow chart in one embodiment of the present invention.
The specific embodiment
Below in conjunction with specific embodiment and accompanying drawing, the invention will be further described.Should be understood that these embodiment only are not used in and limit the scope of the invention for explanation the present invention.
The non-solvent phase separation method uses a kind of intensive polar solvent that just can dissolve at normal temperatures PVDF usually when the preparation casting solution; And that the present invention adopts two kinds of solvents to carry out in preparation during casting solution is composite, and wherein a kind of solvent does not use in the non-solvent phase separation method, and this is the difference that the present invention is different from the non-solvent phase separation method.
Described " part " herein, except specifying, all refer to " weight portion "; Described percentage composition, except specifying, all refer to the quality percentage composition.
Polyvinylidene fluoride hollow fiber membrane of the present invention, its cross section are rendered as the loose spongelike structure that mesh is cross-linked with each other, and the equivalent diameter of mesh is 0.1 ~ 1 μ m.Be limited to 0.1 μ m under the equivalent diameter of mesh, be preferably 0.15,0.2,0.25,0.3,0.35 or 0.4 μ m; Be limited to 1 μ m on it, be preferably 0.95,0.9,0.85,0.8,0.75,0.7,0.65 or 0.6 μ m.If the mesh equivalent diameter is less than 0.1 μ m, the water flux of hollow-fibre membrane is tending towards descending, and affects the wastewater treatment ability; On the other hand, if the mesh equivalent diameter greater than 1 μ m, the separation accuracy of hollow-fibre membrane is tending towards reducing, and likely affects the mechanical strength of hollow-fibre membrane.
Polyvinylidene fluoride in casting solution preparation steps of the present invention (1) is powder, and inherent viscosity η value is 1.8 ~ 2.2, is limited to 1.8 under this value, is preferably 1.9; Be limited to 2.2 on this value, be preferably 2.1 or 2.0.
In casting solution preparation steps of the present invention (1), in the mass percent of casting solution total amount, content of polyvinylidene fluoride is 15% ~ 45%, be preferably 17% ~ 43%, more preferably 20% ~ 41%, more preferably 23% ~ 40%, more preferably 25% ~ 38%, more preferably 25% ~ 35%.
Diluent one in casting solution preparation steps of the present invention (1) is at least a water-soluble polynary ester class that is selected from lower group: acrylic acid carbonic ester, DAA, GBL (gamma-butyrolacton), glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, dihydroxypropane single-ether acetate and their two or more mixtures.
Diluent two in casting solution preparation steps of the present invention (1) is at least a intensive polar solvents that are selected from lower group: dimethyl formamide (DMF), dimethylacetylamide (DMAC), dimethyl sulfoxide (DMSO) (DMSO), acetone (AC), 1-METHYLPYRROLIDONE (NMP), hexamethyl phosphoramide (HMPA), 4-methyl urea (TMU), triethyl phosphate (TEP), trimethyl phosphate (TMP) and their two or more mixtures.
The compound proportion scope of diluent one and diluent two is: diluent one/diluent two=9/1 ~ 1/9 is preferably 8/1 ~ 1/8, more preferably 7/1 ~ 1/7, more preferably 6/1 ~ 1/6, more preferably 5/1 ~ 1/4, more preferably 3/1 ~ 1/3, more preferably 2/1 ~ 1/2.
In the preparation process of hollow-fibre membrane of the present invention (2), extractant used is to be selected from least a in lower group: alcohols, such as unary alcohol, as methyl alcohol, absolute ethyl alcohol etc.; Polyalcohols, as ethylene glycol etc.Alcohols can, separately as extractant, also can be pressed the composite use of different proportion with intensive polar solvents such as dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide etc.Preferred alcohol.
In the preparation process of hollow-fibre membrane of the present invention (2), guarantor hole agent used is alcohols or its aqueous solution, and described alcohols is monohydric alcohol, dihydroxylic alcohols or the trihydroxylic alcohol of 2 ~ 8 carbon atoms; As methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, glycerine etc. and their two or more mixtures, preferred glycerine.
In the preparation process of hollow-fibre membrane of the present invention (2), it is all well-known to those skilled in the art such as temperature is controlled, the time is controlled that the casting solution vacuum defoamation processing of adopting, process spray silk die head form the process conditions that in a doughnut, extractant processing, water, cleaning and dipping, guarantor's hole agent are processed, and by simple test, can determine.
Such as, in a kind of specific embodiment, the operating condition of step (2) is: the casting solution after deaeration is processed is put into the spinning still, under the spinning pressure of measuring pump with the rotating speed of 5 ~ 10 r/min, 0.3 ~ 0.5MPa, from the spinning head that is comprised of two concentric tubes, extrudes; In the dry-spinning path through 0 ~ 200mm, solidify regeneration in the water-bath of 0 ~ 30 ℃ or extractant bath, as-spun fibre passes through twice above two-way (radial and axial) stretching again and appropriateness bounces back, and obtains nascent film.
The hollow-fibre membrane flow sheet can be referring to Fig. 1.
Adopt the hollow-fibre membrane cross section that technique of the present invention is produced to present loose network-like structure, mesh is cross-linked with each other and is evenly distributed, but effective guarantee water flux, mechanical strength and rejection.
Polyvinylidene fluoride hollow fiber membrane of the present invention is applicable to conventional equipment and the operating process that urban water purifies.Fig. 3 has provided hollow-fibre membrane of the present invention and has been used for the flow chart of sewage disposal system.
In experiment, utilize and adopt doughnut film sewage treatment device of the present invention to process urban domestic wastewater, its effluent quality reaches " urban sewage reutilization city miscellaneous water water standard " (GB/T18920-2002).
Embodiment
The polyvinylidene fluoride hollow fiber membrane that following each embodiment is obtained carries out the testing evaluation of following technical indicator.
The cross section microscopic pattern: dry film is after liquid nitrogen Fracture or direct sputtered platinum, with Japanese JSM-5600LV type scanning electron microscope test;
Membrane flux: routinely detection method, such as the method described in following document test: Liu Yongjian etc., " membrane science and technology ", 1998,18(4): 42-45.
Rejection: detection method test routinely, such as can be with reference to the method for describing in following document: Li Nana etc., the research of PVDF/PVA blend film." functional material ", 38 the 12nd phase of volume 1975-1980 pages in 2007.
Ultimate tensile strength: after dry film being cut into the strip of certain size, with Changchun section new WDW3020 type microcomputer, control the test of formula electronic universal tester.
Inherent viscosity (10
2Ml/g): the Ubbelohde viscometer method.
Experiment material: polyvinylidene fluoride (PVDF, model Solef 1015, inherent viscosity η is 1.9 ~ 2.0), U.S. Su Wei company (Solvay)); Other reagent are all available from China Medicine (Group) Shanghai Chemical Reagent Co..
Embodiment 1
(1) by following component and composition batching: polyvinylidene fluoride 18%; Gamma-butyrolacton 41%; Dimethylacetylamide 41%; More than be mass percent.Above-mentioned raw materials is added in intermingling apparatus, and blend forms casting solution under 120 ℃ of blending temperatures.
(2) casting solution after deaeration is processed is put into the spinning still, under the spinning pressure of measuring pump with the rotating speed of 5 r/min, 0.4MPa, from the spinning head that is comprised of two concentric tubes, extrudes; Without dry-spinning path, the fiber that directly will extrude solidifies regeneration in the absolute ethyl alcohol coagulating bath, and as-spun fibre passes through twice above two-way (radial and axial) again and stretches and the appropriateness retraction, obtains as-spun fibre.Carefully will come into being and put into absolute ethyl alcohol extraction 24 hours, and after 2 road pure water cleaning treatment, then protect hole with glycerine and processed 8 hours, both can obtain hollow-fibre membrane.
Film section S EM enlarged drawing is seen Fig. 2, can find out obviously that it presents loose spongelike structure, and mesh is cross-linked with each other, and the equivalent diameter of mesh is 0.3 ~ 1 μ m.
By the performance of the hollow-fibre membrane of above-mentioned process conditions preparation in Table 1.
Embodiment 2
(1) by following component and composition batching: polyvinylidene fluoride 30%; Ethylene glycol monoethyl ether acetate 35%; 1-METHYLPYRROLIDONE 35%; More than be mass percent.Above-mentioned raw materials is added in intermingling apparatus, and blend forms casting solution under 120 ℃ of blending temperatures.
(2) casting solution after deaeration is processed is put into the spinning still, under the spinning pressure of measuring pump with the rotating speed of 5 r/min, 0.4MPa, from the spinning head that is comprised of two concentric tubes, extrudes; Without dry-spinning path, the fiber that directly will extrude solidifies regeneration in the absolute ethyl alcohol coagulating bath, and as-spun fibre passes through twice above two-way (radial and axial) again and stretches and the appropriateness retraction, obtains as-spun fibre.Carefully will come into being and put into absolute ethyl alcohol extraction 24 hours, and after 2 road pure water cleaning treatment, then protect hole with glycerine and processed 8 hours, both can obtain hollow-fibre membrane.
The film cross section presents loose spongelike structure, and the equivalent diameter of the mesh that is cross-linked with each other is that 0.2 ~ 0.9 μ m(is not shown).
By the performance of the hollow-fibre membrane of above-mentioned process conditions preparation in Table 1.
Embodiment 3
(1) by following component and composition batching: polyvinylidene fluoride 40%; DAA 50%; Trimethyl phosphate 10%; More than be mass percent.Above-mentioned raw materials is added in intermingling apparatus, and blend forms casting solution under 120 ℃ of blending temperatures.
(2) casting solution after deaeration is processed is put into the spinning still, under the spinning pressure of measuring pump with the rotating speed of 5 r/min, 0.4MPa, from the spinning head that is comprised of two concentric tubes, extrudes; Without dry-spinning path, the fiber that directly will extrude solidifies regeneration in the absolute ethyl alcohol coagulating bath, and as-spun fibre passes through twice above two-way (radial and axial) again and stretches and the appropriateness retraction, obtains as-spun fibre.Carefully will come into being and put into absolute ethyl alcohol extraction 24 hours, and after 2 road pure water cleaning treatment, then protect hole with glycerine and processed 8 hours, both can obtain hollow-fibre membrane.
The film cross section presents loose spongelike structure, and the equivalent diameter of the mesh that is cross-linked with each other is that 0.2 ~ 1.0 μ m(is not shown).
By the performance of the hollow-fibre membrane of above-mentioned process conditions preparation in Table 1.
Comparative example
Select polyvinylidene fluoride used in embodiment 1,, with reference to the method for introducing in EP1009517, utilize non-solvent phase separation method (NIPS), make the PVDF milipore filter.The performance of the hollow-fibre membrane of preparation is in Table 1.
The performance comparison experiment of the film properties of the PVDF hollow-fibre membrane that distinct methods is prepared and certain urban domestic wastewater of processing sees the following form 1.
As can be seen from Table 1, with PVDF hollow-fibre membrane of the present invention, compare, the standby every film properties of pvdf membrane of NIPS legal system is all poor, and effluent quality does not reach the urban water standard yet.And the prepared pvdf membrane of the embodiment of the present invention has very high separation accuracy in the situation that take into account water flux and tensile strength, and the indices of effluent quality all reached city miscellaneous water water standard, and actual application value is high.Above city miscellaneous water water standard all refers to " urban sewage reutilization city miscellaneous water water standard " (GB/T18920-2002).
Should be understood that those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (9)
1. one kind is used for the polyvinylidene fluoride hollow fiber membrane that urban water purifies, and its cross section is rendered as the spongelike structure that mesh is cross-linked with each other, and the equivalent diameter of mesh is 0.2～1 μ m.
2. polyvinylidene fluoride hollow fiber membrane according to claim 1, is characterized in that, the equivalent diameter of described mesh is 0.2～0.9 μ m.
3. a method for preparing polyvinylidene fluoride hollow fiber membrane according to claim 1 and 2, comprise the steps:
(1) preparation casting solution
Mass percent in the casting solution total amount, be that 1.8～2.2 polyvinylidene fluoride, 5.5%～76.5% diluent one and 5.5%～76.5% diluent two are put into intermingling apparatus with 15%～45% inherent viscosity η, wherein solid matter carries out drying in advance to remove moisture, with mixture 80～120 ℃ of lower agitating heating blend, mixing speed is 70～90r/min, the blend time is 2-24 hour, obtains casting solution
Wherein, described diluent one is at least a water-soluble polynary ester class that is selected from lower group: acrylic acid carbonic ester, DAA, 1,4-butyrolactone, glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, dihydroxypropane single-ether acetate and their two or more mixtures
Described diluent two is at least a solvents that are selected from lower group: dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), acetone, 1-METHYLPYRROLIDONE, hexamethyl phosphoramide, 4-methyl urea, triethyl phosphate, trimethyl phosphate and their two or more mixtures;
(2) the spray silk forms doughnut
With above-mentioned casting solution after the vacuum defoamation of 4-24 hour is processed, adding to depress at nitrogen makes casting solution form doughnut through spray silk die head, then the hollow-fibre membrane that will come into being is put into successively extractant and was processed 5～48 hours, cleaning and dipping 5～48 hours in pure water again, and with protecting the hole agent, process 4-24 hour, obtain the hollow-fibre membrane finished product
Wherein, described extractant is to be selected from least a in lower group: methyl alcohol, ethanol, ethylene glycol, dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide and their two or more mixtures,
Described guarantor hole agent is at least a alcohols or its aqueous solution that is selected from lower group: the monohydric alcohol of 2～8 carbon atoms, dihydroxylic alcohols or trihydroxylic alcohol and their two or more mixtures.
4. method according to claim 3, is characterized in that, described content of polyvinylidene fluoride is 25%～40%.
5. method according to claim 3, is characterized in that, the proportioning of described diluent one and diluent two is: diluent one/diluent two=9/1～1/9.
6. method according to claim 3, is characterized in that, described extractant is ethanol.
7. method according to claim 3, is characterized in that, described alcohols is methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol or glycerine.
8. method according to claim 3, is characterized in that, described alcohols is glycerine.
9. the application of polyvinylidene fluoride hollow fiber membrane according to claim 1 and 2 in urban water purifies.
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| CN103055711B (en) * | 2012-12-28 | 2015-02-25 | 东华大学 | Method for preparing amphiphilic block copolymer modified polyvinylidene fluoride hollow fiber membrane |
| CN107096396B (en) * | 2017-05-19 | 2021-03-19 | 开源环保（集团）有限公司 | Polyvinylidene fluoride hollow fiber microporous filter membrane and preparation method thereof |
| CN116216849A (en) * | 2023-02-24 | 2023-06-06 | 中建八局第四建设有限公司 | Double-film process method for sea water desalination plant |
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| CN101569837A (en) * | 2009-05-26 | 2009-11-04 | 清华大学 | Polyvinylidene fluoride microporous film preparation method |
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| CN101569837A (en) * | 2009-05-26 | 2009-11-04 | 清华大学 | Polyvinylidene fluoride microporous film preparation method |
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| 混合相分离法制备聚偏氟乙烯膜;王建强;《中国优秀硕士学位论文全文数据库工程科技I辑》;20110115(第1期);第16页第2段，第26页图3-4，第27页第1段 * |
| 王建强.混合相分离法制备聚偏氟乙烯膜.《中国优秀硕士学位论文全文数据库工程科技I辑》.2011,(第1期), |
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Effective date of registration: 20170428 Address after: 202450 Shengsi City, Zhoushan Province garden town Yucai Lane No. 6 on the third floor, No. Patentee after: Zhejiang Hai Fu Marine Biotechnology Co., Ltd. Address before: 201620 Shanghai, North Renmin Road, Songjiang District, No. 2999 Patentee before: Donghua University |