CN107551833A - A kind of double modified hollow fiber ultrafiltration membranes and preparation method thereof - Google Patents
A kind of double modified hollow fiber ultrafiltration membranes and preparation method thereof Download PDFInfo
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- CN107551833A CN107551833A CN201710933409.2A CN201710933409A CN107551833A CN 107551833 A CN107551833 A CN 107551833A CN 201710933409 A CN201710933409 A CN 201710933409A CN 107551833 A CN107551833 A CN 107551833A
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- hollow fiber
- fiber ultrafiltration
- ultrafiltration membranes
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- modified hollow
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Abstract
The present invention relates to technical field of membrane separation, discloses a kind of double modified hollow fiber ultrafiltration membranes and preparation method thereof.Double modified hollow fiber ultrafiltration membranes of the present invention are made up of spinning casting solution, coagulation bath and core liquid, and double modified hollow fiber ultrafiltration membranes are hollow tubular, and its section ecto-entad is followed successively by：Outer surface, tube wall and inner surface；The tube wall is asymmetric sponge cavernous structure, and the wall thickness of tube wall is 0.2~0.3mm；The pure water flux of double modified hollow fiber ultrafiltration membranes is more than 700LMH, molecular cut off PEG100000, elongation 200 300%.The film wire good strength of double modified hollow fiber ultrafiltration membranes of the present invention, the hydrophily of film is good, so as to improve the life-span of film and reduce the running cost of component.
Description
Technical field
The present invention relates to technical field of membrane separation, especially a kind of double modified hollow fiber ultrafiltration membranes and preparation method thereof.
Background technology
Membrane separation technique is a kind of new separation technology of green high-efficient, ultrafiltration membrane technique therein have been used to separation,
Concentration, purifying and refined biological product, pharmaceutical products and food, it is additionally operable to blood treatment, wastewater treatment and ultra-pure water and prepares
In terminal processing device.And hollow fiber ultrafiltration membrane is a kind of widely used filter medium, the material that it can be removed includes
Biomolecule, high molecular polymer, colloidal substance, the technical process such as recovery, concentration, extraction can be achieved.
Kynoar (abbreviation PVDF) is a kind of hemihedral crystal shaped polymer, and its glass transition temperature is at -39 DEG C or so, fusing temperature
For degree at 160 DEG C or so, heat decomposition temperature is higher than 316 DEG C.PVDF macromolecular linear chain structure is-CH2CF2-, wherein C-F, C-H and
The respective bond energys of C-C are respectively 453,414.5,347.5KJ/mol.C-C keys are as mass polymerization chain by F atom and H atom bag
Enclose, so that PVDF has splendid chemical stability, heat endurance and mechanical stability.By-CF2- and-CH2- two
Group is alternately arranged, and makes PVDF polarizations, so as to be dissolved in some polar solvents, such as dimethyl acetamide, N- first
Base pyrrolidones, dimethyl sulfoxide (DMSO) and dimethylformamide, this also causes PVDF to turn into one kind and preferably led to non-solvent
Phase inversion prepares the material of pvdf membrane.However, that some limit pvdf membrane further development and answered still be present
With the particularly preparation of the purifying in some sewerages and separation field, for example drinking water, the processing of waste water and biology divide
From etc..Critical problem is as follows：When processing includes the sewage of some natural organic compound such as protein, it is not easy to moisten
Wet pvdf membrane is easily contaminated.Protein is easy to absorption in film surface or blocks film surface apertures, so as to reduce permeability of the membrane
And last separation efficiency, reduce the service life of film, replaced and maintenance cost so as to improve membrane module.
For pvdf membrane on hardly possible wetting easily by protein contamination, a kind of reason likely is the interface in pvdf membrane and water
It there's almost no the association of hydrogen bond.The pvdf membrane surface of hardly possible wetting can produce repulsive interaction to hydrone and along with entropy naturally
Increase, this allows for protein molecule and is easy to envelope adsorption and occupies the superficial layer of film.By contrast, there is the film of hydrophilic layer
With high surface tension so as to by the hydrone of surrounding formed hydrogen bond come film and pollution main body between reconstruct one layer
Thin hydrone circle domain.For the pollutant of some hardly possible wettings, such as some protein, close to hydrosphere and its rule is destroyed
Whole structure is difficult, because this needs ever-increasing energy to remove hydrone circle domain so as to exposure pvdf membrane top layer.
Therefore, the hydrophily of pvdf membrane is improved by various methods so as to improve the life-span of film and reduce the operation of component into
This, just seems significant.In the last few years, some different modes have been tested to adjust pvdf membrane surface.Physical modification
Two major classes, i.e. surface modification and blending and modifying can be divided into.Surface, which is modified, to be typically employed in ready film surface coating or transfers
An one functional layer is connect, wherein except some modification points are in the aperture in film, it is most of to be modified point or in the upper surface of film
Or/and lower surface, this be primarily due to be modified the factor diffuse into it is limited in one's ability in fenestra.Blending and modifying is usually used in film system
The feature of some anticipations is obtained during standby, that is to say, that the modification of film and preparation are that a step is completed in same process,
Just because of this, by the synergy between PVDF and compatible additive, film surface is with having same change in film internal orifice dimension
Property chance.
However, ideal effect is not obtained only with a kind of modification mode to improve the hydrophily of pvdf membrane.
As Chinese patent CN102974238 using film is surface coating modified lifts the hydrophily of milipore filter, but this method of modifying
Due to being mainly combined between film and coat by physical absorption rather than chemical bond, force ratio is weaker, and coat is easy
Come off from film surface, the hydrophily of film gradually weakens during using and cleaning, it is impossible to obtain persistent modified result.
On the other hand, in United States Patent (USP) US6045694 (Cationically charge-modified membranes) using polysulfones as
Matrix membrane material, the copolymer of vinyl pyrrolidone and cation imidazolium compounds is blended into film liquid, is immersed after film forming
Containing modified ethyl polyvinyl and epoxychloropropane modified polyamine, then carry out heat cross-linking or radiation-induced crosslinking prepares lotus
Positive electricity Modified Membrane.But hydrophobic polymer and polymer-modified compatibility are bad, thus limit charged modification degree.
The content of the invention
It is an object of the invention to provide a kind of double modified hollow fiber ultrafiltration membranes and preparation method thereof, to solve existing skill
Pvdf membrane is not because hydrophily is with great difficulty by protein contamination in art, thus membrane lifetime is relatively low, and the higher technology of running cost is asked
Topic.
Therefore, the invention provides a kind of double modified hollow fiber ultrafiltration membranes, it is characterised in that double modified hollow fibres
Dimension milipore filter is made up of spinning casting solution, coagulation bath and core liquid, and double modified hollow fiber ultrafiltration membranes are hollow tubular, and it is disconnected
Face ecto-entad is followed successively by：Outer surface, tube wall and inner surface；The tube wall is asymmetric spongelike structure, and the wall thickness of tube wall is
0.2~0.3mm；The pure water flux of double modified hollow fiber ultrafiltration membranes is more than 700LMH, molecular cut off PEG100000, prolongs
Exhibition rate 200-300%.
Preferably, the fracture strength 4-6Mpa of double modified hollow fiber ultrafiltration membranes, contact angle are less than 50 °.
The present invention also provides a kind of preparation method of double modified hollow fiber ultrafiltration films, it is characterised in that comprises the following steps：
(1) stock up：By percentage by weight be 14%-20% Kynoar, 5%-16% hydrophilic additive and
64%-81% organic solvent mixing, and the percentage by weight of three kinds of raw materials is 100%, is dissolved by heating, then standing and defoaming 24-
48h, obtain spinning casting solution；The polyvinyl alcohol that percentage by weight is 1-10% is added to the water, and the weight of polyethylene alcohol and water
It is 100% to measure percentage sum, heats fully dissolving and obtains coagulation bath,；It is 30%-60% dimethylacetamides by percentage by weight
Amine is added to the water, and dimethyl acetamide and the percentage by weight sum of water are 100%, heats fully dissolving and obtains core liquid；
(2) by the spinning casting solution and core liquid respectively by being pumped into spinneret extrusion molding, spinning-drawing machine is passed through nitrogen
Gas, nitrogen pressure 0.3-0.5MPa；
(3) ultrafiltration membrane filaments of coming into being pass through 1-10cm dry-spinning path, are then mixed with step 1 gained coagulation bath, phase occurs and turns
Change, obtain hollow fiber film yarn；
(4) by ultrafiltration membrane filaments, wire wrapping wheel is wound under 7-20m/min linear velocity；
(5) film wire wound rinses again, dries preservation after being soaked with glycerine-water-antiseptic mixed solution.
Preferably, the hydrophilic additive in the spinning casting solution be polyvinylpyrrolidone, polyethylene glycol, lithium chloride,
Mixed liquor more than one or both of lithium perchlorate, glycerine.
Preferably, the hydrophilic additive in the spinning casting solution is polyvinylpyrrolidone, and its K value is 17 or 30.
Preferably, the organic solvent in the spinning casting solution is dimethylformamide, dimethyl acetamide, dimethyl Asia
Mixed liquor more than one or both of sulfone, 1-METHYLPYRROLIDONE, triethyl phosphate.
Preferably, the percentage by weight of the polyvinyl alcohol in the coagulation bath is 3%-6%.
Preferably, the heating-up temperature that spinning casting solution is prepared described in step 1 is 40-80 DEG C；Coagulation bath is prepared described in step 1
Heating-up temperature be 60-70 DEG C；The heating-up temperature that core liquid is prepared described in step 1 is 20-40 DEG C.
Preferably, dry-spinning path described in step 3 is 1-2cm.
It is further preferred that the temperature of mixed liquor described in step 5 is 20-30 DEG C, soak time 24-48h.
Double modified hollow fiber ultrafiltration membranes of the invention compared with prior art, have the advantages that：
1. integrated use of the present invention surface is modified and blending and modifying lifts the hydrophily of milipore filter, respectively by casting
Polyvinylpyrrolidone is added in film liquid, polyvinyl alcohol is added in coagulation bath, so as to improve the life-span of film and reduce component
Running cost.
2. due to being easily formed hydrogen bond between polyvinylpyrrolidone and polyvinyl alcohol, hydrophilic radical is fixed on film wire table
In face and inner passage, so as to ensure that the steady in a long-term of hydrophilic modifying.
3. due to being easily formed hydrogen bond between polyvinylpyrrolidone and polyvinyl alcohol, this is advantageous to improve phase process
Uniformity, film wire surface is avoided to form macropore, so as to improve the intensity of film wire.
Brief description of the drawings
Fig. 1 is according to the scanning electron microscope image (SEM) in the film section of embodiment 1 under 104 × multiplication factor.
Embodiment
The preparation methods of double modified hollow fiber ultrafiltration membranes of the present invention are prepared in accordance with the following methods, specifically include with
Lower step：
Step 1：Spinning casting solution, coagulation bath and core liquid are prepared according to the dosage of each component in table 1, by PVDF, hydrophilic is added
Add three kinds of raw material mixing of agent and organic solvent (the percentage by weight sum of three kinds of raw materials is 100%), stirred under the conditions of 40-80 DEG C
Mix dissolving 6-12 hours, then standing and defoaming 24-48h, obtain spinning casting solution；Polyvinyl alcohol is added to the water, is heated to 30-70
DEG C, dissolving is sufficiently stirred, obtains coagulation bath；Dimethyl acetamide is added to the water, is then heated to 20-40 DEG C, is sufficiently stirred
Dissolving, obtains core liquid；
Step 2：The casting solution and core liquid are pumped into spinneret extrusion molding by gear respectively, spinning-drawing machine is passed through
Nitrogen, nitrogen pressure 0.3-0.5MPa；
Step 3：Nascent ultrafiltration membrane filaments pass through 1-10cm dry-spinning path, then mix, occur with step 1 gained coagulation bath
Inversion of phases, obtain hollow fiber film yarn；
Step 4：By ultrafiltration membrane filaments, wire wrapping wheel is wound under 7-20m/min linear velocity；
Step 5：The film wire wound rinses again, dries preservation after being soaked with glycerine-water-antiseptic mixed solution.
Table 1 respectively prepares the component and dosage of raw material in embodiment
In above-mentioned preparation embodiment, the hydrophilic additive of spinning casting solution is selected from polyvinylpyrrolidone, polyethylene glycol, chlorine
Change mixture more than one or both of lithium, lithium perchlorate, glycerine.The hydrophilic additive of spinning casting solution is preferably poly-
Vinylpyrrolidone, its K value are 17 or 30.Organic solvent in spinning casting solution is selected from dimethylformamide, dimethylacetamide
Mixture more than one or both of amine, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, triethyl phosphate.
Heating-up temperature when preparing spinning casting solution is 40-80 DEG C, and heating-up temperature is 20-40 DEG C when preparing core liquid.
The amount of polyvinyl alcohol is preferably 3%-6% in coagulation bath.Heating-up temperature is 30-70 DEG C when preparing coagulation bath, preferably
For 60-70 DEG C.
Dry-spinning path is 1-10cm, preferably 1-2cm in step 4.
The temperature of mixed liquor described in step 5 is preferably 20-30 DEG C, and soak time is preferably 24-48h.
The mechanism that the hydrophily and intensity of milipore filter are significantly improved can be construed to：Carbonyl in polyvinylpyrrolidone
Base forms hydrogen bond with the hydroxyl in polyvinyl alcohol, hydrophilic radical is fixed in film wire surface and inner passage, so as to ensure that
Hydrophilic modifying it is steady in a long-term.
Comparative example 1
The preparation of spinning casting solution, the preparation of coagulation bath, the preparation of core liquid and hollow fibre are carried out using the method for embodiment 1
The spinning of milipore filter is tieed up, when difference is that coagulation bath is prepared, non-Polyvinyl alcohol.
The performance comparison of the embodiment of the present invention and comparative example such as table 2.
The performance test results of the comparative example of table 2 and embodiment
| Embodiment/comparative example | Fracture strength (MPa) | Contact angle (degree) |
| Embodiment 1 | 5.5 | 44 |
| Embodiment 2 | 6.1 | 40 |
| Embodiment 3 | 6.4 | 40 |
| Embodiment 4 | 6.0 | 42 |
| Embodiment 5 | 4.8 | 37 |
| Embodiment 6 | 5.0 | 39 |
| Embodiment 7 | 4.6 | 35 |
| Embodiment 8 | 7.5 | 41 |
| Embodiment 9 | 6.6 | 37 |
| Comparative example 1 | 3.2 | 68 |
As shown in Table 2, embodiment 1-9 is compared with comparative example 1, by adding polyvinyl alcohol in coagulation bath, can significantly carry
The fracture strength of high hollow fiber ultrafiltration membrane, contact angle are significantly reduced, and hydrophily significantly improves.
Claims (10)
1. a kind of double modified hollow fiber ultrafiltration membranes, it is characterised in that double modified hollow fiber ultrafiltration membranes are by spinning casting film
Liquid, coagulation bath and core liquid are made, and double modified hollow fiber ultrafiltration membranes are hollow tubular, and its section ecto-entad is followed successively by：
Outer surface, tube wall and inner surface；The tube wall is asymmetric spongelike structure, and the wall thickness of tube wall is 0.2~0.3mm；Double modifications
The pure water flux of hollow fiber ultrafiltration membrane is more than 700LMH, molecular cut off PEG100000, elongation 200-300%.
2. double modified hollow fiber ultrafiltration membranes according to claim 1, it is characterised in that：Double modified doughnuts surpass
The fracture strength 4-6Mpa of filter membrane, contact angle are less than 50 °.
3. the preparation method of double modified hollow fiber ultrafiltration membranes described in a kind of claim 1, it is characterised in that including following step
Suddenly：
(1) stock up：It is 14%-20% Kynoar by percentage by weight, 5%-16% hydrophilic additive and 64%-
81% organic solvent mixing, and the percentage by weight of three kinds of raw materials is 100%, is dissolved by heating, then standing and defoaming 24-48h, obtain
To spinning casting solution；The polyvinyl alcohol that percentage by weight is 1-10% is added to the water, and the weight percent of polyethylene alcohol and water
It is that 100%, 30-70 DEG C of heating fully dissolving obtains coagulation bath than sum,；It is 30%-60% dimethyl second by percentage by weight
Acid amides is added to the water, and dimethyl acetamide and the percentage by weight sum of water are 100%, heats fully dissolving and obtains core liquid；
(2) by the spinning casting solution and core liquid respectively by being pumped into spinneret extrusion molding, spinning-drawing machine is passed through nitrogen, nitrogen
Atmospheric pressure is 0.3-0.5MPa；
(3) ultrafiltration membrane filaments of coming into being pass through 1-10cm dry-spinning path, are then mixed with step 1 gained coagulation bath, inversion of phases occurs,
Obtain hollow fiber film yarn；
(4) ultrafiltration membrane filaments are wound under 7-20m/min linear velocity by wire wrapping wheel；
(5) film wire wound rinses again, dries preservation after being soaked with glycerine-water-antiseptic mixed solution.
4. according to double preparation methods for being modified hollow fiber ultrafiltration membranes described in claim 3, it is characterised in that：The spinning
Hydrophilic additive in casting solution is polyvinylpyrrolidone, one kind in polyethylene glycol, lithium chloride, lithium perchlorate, glycerine
Or two or more mixed liquor.
5. according to double preparation methods for being modified hollow fiber ultrafiltration membranes described in claim 3, it is characterised in that：The spinning
Hydrophilic additive in casting solution is polyvinylpyrrolidone, and its K value is 17 or 30.
6. according to double preparation methods for being modified hollow fiber ultrafiltration membranes described in claim 3, it is characterised in that：The spinning
Organic solvent in casting solution is dimethylformamide, dimethyl acetamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, phosphoric acid
Mixed liquor more than one or both of triethyl.
7. according to double preparation methods for being modified hollow fiber ultrafiltration membranes described in claim 3, it is characterised in that：The gel
The percentage by weight of polyvinyl alcohol in bath is 3%-6%.
8. according to double preparation methods for being modified hollow fiber ultrafiltration membranes described in claim 3, it is characterised in that：Step 1 institute
The heating-up temperature for stating preparation spinning casting solution is 40-80 DEG C；The heating-up temperature that coagulation bath is prepared described in step 1 is 60-70 DEG C；Step
Rapid 1 heating-up temperature for preparing core liquid is 20-40 DEG C.
9. according to double preparation methods for being modified hollow fiber ultrafiltration membranes described in claim 3, it is characterised in that：Step 3 institute
It is 1-2cm to state dry-spinning path.
10. the preparation method of double modified hollow fiber ultrafiltration membranes according to claim 3, it is characterised in that：Described in step 5
The temperature of mixed liquor is 20-30 DEG C, soak time 24-48h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108715801A (en) * | 2018-06-01 | 2018-10-30 | 苏州凯虹高分子科技有限公司 | A kind of cell separation filter core and preparation method thereof |
| CN108854602A (en) * | 2018-06-28 | 2018-11-23 | 江苏泓膜业科技有限公司 | A kind of enhanced hollow fiber ultrafiltration membrane and preparation method thereof |
| CN111921384A (en) * | 2020-08-11 | 2020-11-13 | 浙江易膜新材料科技有限公司 | Casting membrane liquid of PVDF hollow fiber ultrafiltration membrane, spinning mechanism and production method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1418723A (en) * | 2002-07-19 | 2003-05-21 | 东华大学 | Large flux polyvinyl chlorid doughnut film, and its mfg. method |
| CN105363350A (en) * | 2014-08-31 | 2016-03-02 | 海南立昇净水科技实业有限公司 | Unsymmetrical chlorine-containing polymer-based charged type hollow fiber filtration membrane and preparation method thereof |
-
2017
- 2017-10-10 CN CN201710933409.2A patent/CN107551833B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1418723A (en) * | 2002-07-19 | 2003-05-21 | 东华大学 | Large flux polyvinyl chlorid doughnut film, and its mfg. method |
| CN105363350A (en) * | 2014-08-31 | 2016-03-02 | 海南立昇净水科技实业有限公司 | Unsymmetrical chlorine-containing polymer-based charged type hollow fiber filtration membrane and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108715801A (en) * | 2018-06-01 | 2018-10-30 | 苏州凯虹高分子科技有限公司 | A kind of cell separation filter core and preparation method thereof |
| CN108854602A (en) * | 2018-06-28 | 2018-11-23 | 江苏泓膜业科技有限公司 | A kind of enhanced hollow fiber ultrafiltration membrane and preparation method thereof |
| CN111921384A (en) * | 2020-08-11 | 2020-11-13 | 浙江易膜新材料科技有限公司 | Casting membrane liquid of PVDF hollow fiber ultrafiltration membrane, spinning mechanism and production method thereof |
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| CN107551833B (en) | 2019-10-29 |
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