CN102430344A - Hollow polyvinylidene fluoride fibrous membrane and preparation method as well as application thereof - Google Patents
Hollow polyvinylidene fluoride fibrous membrane and preparation method as well as application thereof Download PDFInfo
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- CN102430344A CN102430344A CN201110348044XA CN201110348044A CN102430344A CN 102430344 A CN102430344 A CN 102430344A CN 201110348044X A CN201110348044X A CN 201110348044XA CN 201110348044 A CN201110348044 A CN 201110348044A CN 102430344 A CN102430344 A CN 102430344A
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Abstract
The invention discloses a hollow polyvinylidene fluoride fibrous membrane for industrial sewage treatment and a preparation method of the fibrous membrane as well as application of the fibrous membrane; and the cross section of the hollow polyvinylidene fluoride fibrous membrane is a spongy structure which is provided with mutually crosslinked mesh openings, and the equivalent diameter of the mesh openings is 1-3mum.
Description
Technical field
The present invention relates to a kind of polyvinylidene fluoride hollow-fibre membrane that is used for Industrial Wastewater Treatment, its preparation method and in Application in Industrial Wastewater Treatment.
Technical background
Membrane separation technique has separative efficiency height, easy to operate, facility compact and advantage such as energy-conservation, compares with other conventional art, and it is all having outstanding behaviours aspect the regeneration of bio-medical, environmental protection and water resource.Polyvinylidene fluoride (PVDF) is a kind of novel hemihedral crystal shape fluorocarbon thermoplastic organic fluorine material; Series of advantages such as have that hot property is stable, good mechanical property, anticorrosive, anti-wriggling property are good; Also have outstanding anti-aging characteristic and uvioresistant ability simultaneously; And easy casting film-forming is a kind of good material of preparing that development in recent years is got up.
About the preparation method of polyvinylidene fluoride separation membrane material, at present that main usefulness is non-solvent phase separation method (NIPS), and domestic also have correlative study person to be referred to as phase inversion method or immerse the precipitated phase conversion method, and many documents and patent all have relevant report.For the non-solvent phase separation method, Mei Zhang etc. are at Journal of Membrane Science, and 2008, introduced among the 319:169-175 and utilized the non-solvent phase separation method to obtain the PVDF milipore filter that inside is the finger-like pore structure for solvent through adopting DMSO; EP1009517 adopts the non-solvent phase separation method to make the hydrophily or the hydrophobicity asymmetry polyvinylidene fluoride microporous film of high porosity.The microporous barrier that the non-solvent phase separation method prepares is an anisotropic membrane all generally, and demonstrates the finger-like macroporous structure more, though this structure can make film forming have higher flux, also can reduce the mechanical strength and the rejection of film forming accordingly.
Summary of the invention
For overcoming the above-mentioned defective of the prepared polyvinylidene fluoride separation membrane material of existing non-solvent phase separation method; The present invention is the basis with the mechanism that is separated, and works out a kind of new method that can prepare the polyvinylidene fluoride hollow-fibre membrane with good mechanical strength, high flux and high rejection.
Therefore, one of the object of the invention is to provide a kind of polyvinylidene fluoride hollow-fibre membrane that can be used for Industrial Wastewater Treatment.
Another object of the present invention is to provide a kind of method for preparing the polyvinylidene fluoride hollow-fibre membrane.
A purpose more of the present invention is to provide above-mentioned polyvinylidene fluoride hollow-fibre membrane in Application in Industrial Wastewater Treatment.
For realizing above-mentioned purpose, the present invention adopts following technical scheme:
A kind of polyvinylidene fluoride hollow-fibre membrane that is used for Industrial Wastewater Treatment, its cross section is rendered as the spongelike structure that mesh is cross-linked with each other, and the equivalent diameter of mesh is 1 ~ 3 μ m.
A kind of method for preparing above-mentioned polyvinylidene fluoride hollow-fibre membrane; Comprise polyvinylidene fluoride powder and two kinds of organic liquid blending; The blend of gained is heated blend under the temperature that is higher than 10 ~ 50 ℃ of polymer powders fusing points; And extrude the doughnut form of processing through certain die head, and put into specific organic solvent again and soak so that extract above-mentioned two kinds of organic liquids, handle and obtaining finished film through clean and protect the hole agent behind the certain hour again through pure water.
Particularly, polyvinylidene fluoride doughnut membrane preparation method of the present invention comprises the steps:
(1) preparation casting solution
In the mass percent of casting solution total amount, the polyvinylidene fluoride with 20% ~ 45% (powder, η=1.5 ~ 2.0), 5.5% ~ 72% diluent A and 5.5% ~ 72% diluent B are put into intermingling apparatus; Wherein solid matter carries out drying in advance to remove moisture, and 170 ~ 220 ℃ of following agitating heating blend, mixing speed is 90 ~ 120r/min with mixture; The blend time is 0.5-8 hour; Preferred 2-6 hour, more preferably 3-4 hour, obtain casting solution;
(2) the spray silk forms doughnut
With above-mentioned casting solution through 0.5-8 hour, preferred 2-6 hour, after more preferably 3-4 hour vacuum defoamation is handled, under nitrogen pressure, make casting solution form a doughnut through spray silk die head, then nascent hollow-fibre membrane is put into extractant successively and handled 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 hole agent processing 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-fibre membrane of the present invention both can make film have higher water flux, can make film have good mechanical strength and higher rejection simultaneously again, was applicable to fully to be used for Industrial Wastewater Treatment.
Description of drawings
Fig. 1 is the hollow-fibre membrane flow sheet in one embodiment of the present invention.Wherein, 1 is dissolution kettle, and 2 is filter, and 3 is material-storage jar, and 4 is measuring pump, and 5 is spinneret, and 6 is outer coagulating bath, and 7 is first rinsing bowl, and 8 is second rinsing bowl, and 9 is the 3rd rinsing bowl, and 10 is up-coiler.
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 present invention is described further.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.
The solvent that the non-solvent phase separation method uses when the preparation casting solution is the intensive polar solvent that just can dissolve PVDF at normal temperatures; The solvent that the present invention adopts when the preparation casting solution then can not dissolve PVDF at normal temperatures, only under certain hot conditions, could dissolve PVDF, and this is the difference that the present invention is different from the non-solvent phase separation method.
" part " described in this paper except that specifying, all refers to " weight portion "; Described percentage composition except that specifying, all refers to the quality percentage composition.
Polyvinylidene fluoride hollow-fibre 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 1 ~ 3 μ m.The following 1 μ m that is limited to of mesh equivalent diameter is preferably 1.1,1.2,1.3,1.4,1.5,1.6,1.7 or 1.8 μ m; Be limited to 3 μ m on it, be preferably 2.9,2.8,2.7,2.6,2.5,2.3,2.4 or 2.2 μ m.If the mesh equivalent diameter is less than 1 μ m, then the water flux of hollow-fibre membrane is tending towards descending, and influences the wastewater treatment ability; On the other hand, if the mesh equivalent diameter greater than 3 μ m, then the rejection of hollow-fibre membrane is tending towards reducing, and might influence the mechanical strength of hollow-fibre membrane.
Polyvinylidene fluoride in the casting solution preparation steps of the present invention (1) is a powder, and inherent viscosity is that the η value is 1.4 ~ 2.0, and the following of this value is limited to 1.4, is preferably 1.5,1.6 or 1.7; Be limited to 2.0 on this value, be preferably 1.9 or 1.8.
In the casting solution preparation steps of the present invention (1), in the mass percent of casting solution total amount, content of polyvinylidene fluoride is 20% ~ 45%; Be preferably 22% ~ 43%, more preferably 25% ~ 41%, more preferably 27% ~ 40%; More preferably 30% ~ 38%, more preferably 30% ~ 35%.
Diluent A in the casting solution preparation steps of the present invention (1) is at least a polynary ester class that is selected from down in the group: gamma-butyrolacton (γ-BL), glycerol triacetate (GTA), repefral (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP).
Diluent B in the casting solution preparation steps of the present invention (1) be selected from down the group at least a: phthalic acid two (2-ethylhexyl) ester (DEHP), benzophenone (DPK), diphenyl carbonate (DPC), diphenyl ether (DPE), di-n-octyl sebacate (DOS), dioctyl adipate (DOA), terephthalic acid (TPA) di-isooctyl (DOTP).
The compound proportion scope of diluent A and diluent B is: diluent A/ diluent B=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); Used extractant is can dissolve the ester class but the polyalcohol or other organic solvent that do not destroy pvdf membrane, such as being to be selected from down at least a in the group: methyl alcohol, ethanol, propyl alcohol, butanols, octanol, n-hexane, acetone, ethyl acetate, isoamyl acetate and their two or more mixtures.Preferred alcohol.
In the preparation process of hollow-fibre membrane of the present invention (2), used guarantor hole agent be selected from down the group at least a: triethylene-glycol (triethylene glycol), ethylene glycol (EG), glycerine higher boiling alcohols and their two or more mixtures such as (glycerine).Preferred glycerine.
In the preparation process of hollow-fibre membrane of the present invention (2); It all is well-known to those skilled in the art such as temperature control, time control that the casting solution vacuum defoamation processing of being adopted, process spray silk die head form the process conditions that cleaning and dipping, guarantor's hole agent are handled in a doughnut, extractant processing, the water, can confirm through simple test.
Such as; In a kind of specific embodiment; The operating condition of step (2) is: the casting solution after deaeration is handled is put into the spinning still, under the spinning pressure of measuring pump with the rotating speed of 5 ~ 20 r/min, 0.4 ~ 0.6MPa, extrudes from the spinning head of being made up of two concentric tubes; In dry-spinning path through 0 ~ 300mm, in 0 ~ 60 ℃ water-bath or extractant bath, solidify regeneration, as-spun fibre passes through two-way more than the twice (radial and axial) again and stretches and the appropriateness retraction, obtains the film of coming into being.
The hollow-fibre membrane flow sheet can be referring to Fig. 1.
The hollow-fibre membrane cross section of adopting technology of the present invention to produce demonstrates loose network-like structure, and mesh is cross-linked with each other and is evenly distributed, and can effectively ensure water flux, mechanical strength and rejection.
Polyvinylidene fluoride hollow-fibre membrane of the present invention is applicable to the conventional equipment and the operating process of Industrial Wastewater Treatment.Fig. 3 has provided the flow chart that hollow-fibre membrane of the present invention is used for sewage disposal system.
In experiment, utilize and adopt doughnut film sewage treatment device of the present invention to handle leather-making industrial wastewater, its effluent quality reaches " urban sewage reutilization water quality standard for industries " (GB/T19923-2005).
Embodiment
The polyvinylidene fluoride hollow-fibre 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 cleaved or direct sputtered platinum, with Japanese JSM-5600LV type scanning electron microscope test;
Membrane flux: by the conventional sense method, such as the method test of describing in the following document: Liu Yongjian etc., " membrane science and technology ", 1998,18 (4): 42-45.
Rejection: by conventional sense method test, such as can be with reference to the method for describing in the following document: Li Nana etc., the research of PVDF/PVA blend film." functional material ", 2007 38 volume the 12nd phase 1975-1980 pages or leaves.
Ultimate tensile strength: after dry film being cut into the strip of certain size, with the new WDW3020 type system controlled by computer formula electronic universal tester test of Changchun section.
Inherent viscosity (10
2Ml/g): the Ubbelohde viscometer method.
Experiment material: polyvinylidene fluoride (PVDF, model FR904, inherent viscosity η are 1.7), Shanghai three Ai Fu companies); Other reagent are all available from China Medicine (Group) Shanghai Chemical Reagent Co..
Embodiment 1
(1) prepares burden with forming by following component: polyvinylidene fluoride 30%; Triacetyl glycerine 28%; Phthalic acid two (2-ethylhexyl) ester 42%; More than be mass percent.Above-mentioned raw materials is added in the intermingling apparatus, and blend forms casting solution under 180 ℃ of blending temperatures.
(2) casting solution after deaeration is handled is put into the spinning still, under the spinning pressure of measuring pump with the rotating speed of 10 r/min, 0.5MPa, extrudes from the spinning head of being made up of two concentric tubes; Without dry-spinning path, directly the fiber of extruding is solidified regeneration in the absolute ethyl alcohol coagulating bath, as-spun fibre passes through two-way more than the twice (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 clean, protect the hole with glycerine again and handled 8 hours, obtain hollow-fibre membrane.
Film section S EM enlarged drawing is seen Fig. 2, can find out obviously that it demonstrates loose spongelike structure, and mesh is cross-linked with each other, and the equivalent diameter of mesh is 1 ~ 3 μ m.
Performance by the hollow-fibre membrane of above-mentioned process conditions preparation is seen table 1.
Embodiment 2
(1) prepares burden with forming by following component: polyvinylidene fluoride 40%; Gamma-butyrolacton 45%; Benzophenone 15%; More than be mass percent.Above-mentioned raw materials is added in the intermingling apparatus, and blend forms casting solution under 180 ℃ of blending temperatures.
(2) casting solution after deaeration is handled is put into the spinning still, under the spinning pressure of measuring pump with the rotating speed of 10 r/min, 0.5MPa, extrudes from the spinning head of being made up of two concentric tubes; Without dry-spinning path, directly the fiber of extruding is solidified regeneration in the absolute ethyl alcohol coagulating bath, as-spun fibre passes through two-way more than the twice (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 clean, protect the hole with glycerine again and handled 8 hours, obtain hollow-fibre membrane.
The film cross section demonstrates loose spongelike structure, and the equivalent diameter of the mesh that is cross-linked with each other is 1.2 ~ 3 μ m (not shown).
Performance by the hollow-fibre membrane of above-mentioned process conditions preparation is seen table 1.
Embodiment 3
(1) prepares burden with forming by following component: polyvinylidene fluoride 42%; Dibutyl phthalate 25%; Diphenyl carbonate 33%; More than be mass percent.Above-mentioned raw materials is added in the intermingling apparatus, and blend forms casting solution under 180 ℃ of blending temperatures.
(2) casting solution after deaeration is handled is put into the spinning still, under the spinning pressure of measuring pump with the rotating speed of 10 r/min, 0.5MPa, extrudes from the spinning head of being made up of two concentric tubes; Without dry-spinning path, directly the fiber of extruding is solidified regeneration in the absolute ethyl alcohol coagulating bath, as-spun fibre passes through two-way more than the twice (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 clean, protect the hole with glycerine again and handled 8 hours, obtain hollow-fibre membrane.
The film cross section demonstrates loose spongelike structure, and the equivalent diameter of the mesh that is cross-linked with each other is 1.1 ~ 2.9 μ m (not shown).
Performance by the hollow-fibre membrane of above-mentioned process conditions preparation is seen table 1.
Comparative example
Select polyvinylidene fluoride used among the embodiment 1 for use,, utilize non-solvent phase separation method (NIPS), make the PVDF milipore filter with reference to the method for introducing among the EP1009517.The performance of the hollow-fibre membrane of preparation is seen table 1.
The film properties of the PVDF hollow-fibre membrane that distinct methods is prepared sees the following form with the performance comparison experiment of handling leather-making waste water.
Can find out from table 1, compare with PVDF hollow-fibre membrane of the present invention that pvdf membrane each item film properties of NIPS method preparation is all relatively poor, effluent quality does not reach the industrial reuse standard yet.And the prepared pvdf membrane of the embodiment of the invention has the pure water flux of superelevation under the situation of taking into account rejection and tensile strength, and each item index of effluent quality all reached the industrial reuse standard, and actual application value is high.Above industrial reuse standard all refers to " urban sewage reutilization water quality standard for industries " (GB/T19923-2005).
Should be understood that those skilled in the art can do various changes or modification to 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 institute restricted portion equally.
Claims (10)
1. polyvinylidene fluoride hollow-fibre membrane that is used for Industrial Wastewater Treatment, its cross section is rendered as the spongelike structure that mesh is cross-linked with each other, and the equivalent diameter of mesh is 1 ~ 3 μ m.
2. polyvinylidene fluoride hollow-fibre membrane according to claim 1 is characterized in that, the equivalent diameter of said mesh is 1.1 ~ 2.9 μ m.
3. polyvinylidene fluoride hollow-fibre membrane according to claim 1 is characterized in that, the equivalent diameter of said mesh is 1.2 ~ 2.8 μ m.
4. a method for preparing according to each described polyvinylidene fluoride hollow-fibre membrane in the claim 1 to 3 comprises the steps:
(1) preparation casting solution
Mass percent in the casting solution total amount; Inherent viscosity with 20% ~ 45% is that 1.4 ~ 2.0 polyvinylidene fluoride, 5.5% ~ 72% diluent A and 5.5% ~ 72% diluent B are put into intermingling apparatus, and wherein solid matter carries out drying in advance to remove moisture, with mixture 170 ~ 220 ℃ of following agitating heating blend; Mixing speed is 90 ~ 120 r/min; The blend time is 0.5-8 hour, obtains casting solution
Wherein, said diluent A be selected from down the group at least a: gamma-butyrolacton, glycerol triacetate, repefral, diethyl phthalate, dibutyl phthalate,
Said diluent B be selected from down the group at least a: phthalic acid two (2-ethylhexyl) ester, benzophenone, diphenyl carbonate, diphenyl ether, di-n-octyl sebacate, dioctyl adipate, terephthalic acid (TPA) di-isooctyl;
(2) the spray silk forms doughnut
After 0.5-8 hour vacuum defoamation of above-mentioned casting solution process processing; Under nitrogen pressure, make casting solution form doughnut through spray silk die head; Then nascent hollow-fibre membrane is put into extractant successively and handled 5 ~ 48 hours, cleaning and dipping 5 ~ 48 hours in pure water again, and with protecting hole agent processing 4-24 hour; Obtain the hollow-fibre membrane finished product
Wherein, said extractant be selected from down the group at least a: methyl alcohol, ethanol, propyl alcohol, butanols, octanol, n-hexane, acetone, ethyl acetate, isoamyl acetate and their two or more mixtures,
Said guarantor hole agent be selected from down the group at least a: triethylene-glycol, ethylene glycol, glycerine and their two or more mixtures.
5. method according to claim 4 is characterized in that, said content of polyvinylidene fluoride is 25% ~ 41%.
6. method according to claim 4 is characterized in that, the proportioning of said diluent A and diluent B is: diluent A/ diluent B=9/1 ~ 1/9.
7. method according to claim 4 is characterized in that said extractant is an ethanol.
8. method according to claim 4 is characterized in that, said guarantor hole agent is a glycerine.
According to each described polyvinylidene fluoride hollow-fibre membrane in the claim 1 to 3 in Application in Industrial Wastewater Treatment.
10. application according to claim 9 is characterized in that said industrial wastewater is a leather-making waste water.
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| CN103521092A (en) * | 2013-10-18 | 2014-01-22 | 国家海洋局天津海水淡化与综合利用研究所 | Environment-friendly method for preparing fluorine-containing polymer microporous film |
| CN103787884A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Ternary extractant and its application, and method for extracting antioxidant 1010 from polyolefin material |
| CN104548653A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Quaternary extractant, application thereof, and method for extracting antioxidant from polyolefin |
| CN109336764A (en) * | 2018-11-28 | 2019-02-15 | 四川久润环保科技有限公司 | A kind of ethyl alcohol, diphenyl carbonate, the separation method of dibutyl ester mixture and system |
| CN110605032A (en) * | 2018-06-16 | 2019-12-24 | 苏州五颗星特种超滤膜科技有限公司 | Preparation method of finishing type hollow fiber membrane |
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| CN110605032A (en) * | 2018-06-16 | 2019-12-24 | 苏州五颗星特种超滤膜科技有限公司 | Preparation method of finishing type hollow fiber membrane |
| CN109336764A (en) * | 2018-11-28 | 2019-02-15 | 四川久润环保科技有限公司 | A kind of ethyl alcohol, diphenyl carbonate, the separation method of dibutyl ester mixture and system |
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Application publication date: 20120502 |