CN105854625A - Preparation method of unpowered PVDF hollow fiber membrane - Google Patents
Preparation method of unpowered PVDF hollow fiber membrane Download PDFInfo
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- CN105854625A CN105854625A CN201610423496.2A CN201610423496A CN105854625A CN 105854625 A CN105854625 A CN 105854625A CN 201610423496 A CN201610423496 A CN 201610423496A CN 105854625 A CN105854625 A CN 105854625A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The invention discloses a preparation method of an unpowered PVDF hollow fiber membrane, and belongs to the technical field of membrane separation. The preparation method comprises the steps that polyvinylidene fluoride (PVDF) serves as the main membrane material, blending modification is conducted on PVDF and inorganic additives, the surface of a functional fiber support tube is coated with a modified PVDF membrane casting solution through a functional fiber support tube, and then the unpowered PVDF membrane is obtained. The unpowered PVDF membrane is applied to treatment of industrial and agricultural polluted wastewater and drinking water. The unpowered PVDF hollow fiber membrane has good hydrophilic performance, the deficiency that a traditional membrane material needs the external pressure condition for water outflow is changed, the functional fiber support tube has a high binding capacity with PVDF, the prepared PVDF membrane is high in mechanical strength and good in hydrophilia, the production process is simple, the cost is low, and the membrane has a wide application prospect.
Description
Technical field
The invention belongs to technical field of membrane separation, relate in the unpowered PVDF of a kind of inorganic additive modification PVDF
Hollow fiber membrane preparation method, this PVDF hollow-fibre membrane can apply to industrial wastewater, sanitary wastewater and drinking water treatment
Industry, production cost is low, efficiency is high, it is not necessary to external pressure, and service life is long.
Background technology
China is the country that a hydropenia is serious, and water resources ownership per capita is few, and industrial or agricultural water consumption is big, in recent years, along with
Expanding economy, inevitably causes water pollution, including heavy metal pollution, organic contamination, bacterial virus pollution etc.,
Having had a strong impact on human health, destroyed ecological environment, therefore, scientific and effective solution water pollution problems is extremely the most urgent.
Membrane separation technique because efficiency is high, simple to operate, low cost and other advantages, be widely used in current water treatment field and
More ripe.PVDF is a kind of acid-alkali-corrosive-resisting, high temperature resistant, the material of resistance to oxidation, ultra-violet radiation resisting, is employed more
In the preparation of membrane material, but PVDF itself has hydrophobicity, and antifouling property is poor, runs and in backwash process to film
Requirement of mechanical strength high, and need ambient pressure to provide power, add production cost, be blended with modified inorganic additive
After, hydrophilic and the antifouling property of PVDF can be effectively improved, be coated to functional fibre liner surface and the PVDF that is prepared as
Membrane material, mechanical strength is high, difficult drop-off, substantially increases the service life of film, and can water outlet under the conditions of unpowered,
Reducing production cost, effectively simplified operating procedure, backwash process is simple, it is not necessary to chemical reagent cleans.
Chinese patent CN1011319081A discloses the preparation method of a kind of large-flux anti-pollution PVDF hollow-fibre membrane,
After the PVDF hollow-fibre membrane ethanol prepared or sodium hypochlorite being processed, acrylic acid aqueous solution carries out γ-penetrate
Line irradiation grafting, utilize in acrylic molecules-COOH group improves the hydrophilicity of film, water flux has had and has been greatly improved,
But in preparation process, PVDF hollow-fibre membrane is inevitably processed the impact of liquid so that the service life reduction of film,
And the mechanical strength of film is low relative to fiber liner tube type PVDF hollow-fibre membrane.
Chinese patent CN101254420A]Disclose the preparation method of a kind of reinforcement tubular porous composite film, in reinforced pipe
Fill high viscosity water dissolubility implant, it is to avoid casting solution penetrates in reinforced pipe, blocks fenestra, outside applied in two coats casting
Film liquid, it is ensured that film surface does not haves defect, the permeable amount of film is big, but fills high viscosity water soluble substance in reinforced pipe
Operating difficulties, wastes material, and prepared membrane material remains a need for impressed pressure and provides power.
European patent EP 1321178B1 discloses the preparation method of a kind of braided tube enhancement type hollow fiber film, by macromolecule
Resin is dissolved in organic solvent (dimethylformamide or dimethyl acetylamide etc.), is simultaneously introduced polyvinylpyrrolidone and hydrophilic
Property compound, as additive, utilizes spinning technique to apply resin to fiber reinforcement tube-surface, and be prepared for good water permeability,
The enhancement type hollow fiber film that rejection is high, mechanical strength is high, but prepared hollow-fibre membrane needs ambient pressure to provide power,
Macromolecule resin is coated to reinforced pipe surface and easily comes off.
Chinese patent CN1829597A discloses the preparation method of a kind of zero defect composite membrane, and the method is bonded by introducing
Macromolecule resin is adhered to braided tube surface by agent, multiple entry spinneret coating multiple casting solution simultaneously, weaves in spinning process
The internal evacuation of pipe, strengthens the combination of coating fluid and braided tube, and prepared membrane material peel strength is remarkably reinforced, but multilamellar
Coating fluid can reduce the permeability of film, evacuation in braided tube, virtually adds the difficulty of preparation technology, is unfavorable for industry
Metaplasia is produced.
Chinese patent CN1864828A discloses the preparation side of a kind of reticular fiber reinforced hollow fiber membrane of polyvinylidene fluoride
Method, is first spun into hollow fiber conduit by PVDF casting solution, at one layer of fleece of hollow fiber conduit surface weave, to increase
Add intensity, then coat one layer of pvdf membrane in web surface, constitute the enhancement mode PVDF doughnut of three-decker
Film, preparation process is relatively complicated, and intermediate layer fleece overlapping operation difficulty, multiple structure reduces the permeability of film.
Summary of the invention
The present invention is directed to the series of problems that current PVDF hollow-fibre membrane exists, it is provided that a kind of novel preparation method,
Loaded down with trivial details to solve to prepare membrane material process in above-mentioned patent, resin is in shortcomings such as the peel strength of fiber liner surface are low, simultaneously
Overcome conventional film material to need external pressure to provide the deficiency of power, to be preferably applied for the process of industrial and agricultural wastewater, alleviate water dirty
Dye present situation, is blended modified inorganic additive with PVDF, through spinning technique, PVDF casting solution is coated to functional fibre
Liner surface, is prepared as unpowered PVDF hollow-fibre membrane through inversion of phases, and mechanical strength is high, good hydrophilic property, it is possible to
Realize unpowered under the conditions of water outlet, reduce production cost, backwash process is simple, it is not necessary to chemical agent clean.
Described unpowered PVDF hollow-fibre membrane, is first modified inorganic additive, improve hydrophilic, strengthen with
The adhesion of PVDF resin, described modifying agent is coupling agent, and lysate is certain density ethanol solution, obtains modified nothing
Machine additive, is then blended with PVDF, and spinning.
The preparation method of a kind of unpowered PVDF hollow-fibre membrane is carried out in the steps below:
Step one, inorganic additive is added in ethanol solution (volumetric concentration 15%～40% of ethanol solution), (50～
80) with (250～350) r/min magnetic agitation (0.5～1) h under DEG C water bath with thermostatic control, coupling agent, cooling water backflow are added
Reaction (3～5) h, filter, filtering residue ethanol solution washing (3～5) secondary, under the conditions of 60～90 DEG C be vacuum dried (3～
5)h。
Step 2, step one is processed after inorganic additive add in organic solvent, at (40～70) DEG C water bath with thermostatic control bar
Under part, with frequency ultrasound vibration (0.5～2) h of (10～40) KHz, it is subsequently adding porogen, then in (50～90)
Under the conditions of DEG C water bath with thermostatic control, mechanical agitation (2～6) h, add PVDF powder, continue at (50～90 DEG C) constant temperature
Heating in water bath, mechanical agitation (6～13) h, obtain casting solution；
Casting solution is poured into the material storage kettle tank of spinning-drawing machine and seals by step 3, under the conditions of (50～90) DEG C heated at constant temperature, uses vacuum
System vacuum is evacuated to 0.04～0.1MPa by pump, standing and defoaming 4～8h, is then filled with nitrogen to material storage kettle tank, adjusts storage
Material still pressure tank is 0.05～0.3MPa, and coagulation bath temperature is 30～50 DEG C, opens dosing pump, with (6～16) mL/min
Speed extrusion casting solution, setting air spacing is (0.1～0.5) m, and functional fibre bushing pipe hub rotation speed is (6～12) r/min,
Wire winding speed keeps consistent with functional fibre bushing pipe wheel hub, and casting solution is coated with through spinneret and is uniformly layed onto function liner surface, solidifying
Gu in Yu through inversion of phases film-forming, the membrane material prepared is cut off, is placed in Rinsing Area immersion (24～36) h,
At room temperature dry after taking-up.
In step one, inorganic additive is (0.5～1) with the mass ratio of coupling agent: 1.
Inorganic additive described in step one is kieselguhr, silicon dioxide, Kaolin, alchlor, calcium carbonate, titanium dioxide
Or clay.
The particle diameter of inorganic additive described in step one is 500～3000nm.
The mass fraction in ethanol solution of inorganic additive described in step one is 5%～15%.
Coupling agent described in step one is VTES, vinyl three ('beta '-methoxy ethyoxyl) silane, γ-ammonia
Propyl trimethoxy silicane, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, isopropyl two oleic acid acyloxy (two
Octylphosphonic acid acyloxy) titanate esters, monoalkoxy insatiable hunger or fat acid titanate esters.
Organic solvent described in step 2 is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide or N-first
Base ketopyrrolidine, the mass fraction in casting solution of the additive after step one process is 0.5%～5%.
Porogen described in step 2 is PEG400, Macrogol 600, PEG20000, polyvinylpyrrolidine
Ketone K30, lithium chloride or sodium chloride, additive quality is the 2%～8% of casting solution gross mass.
Step 2 PVDF mass fraction in casting solution is 13%～19%.
Functional fibre bushing pipe described in step 3 is to be formed by different fibrous materials braidings, fibrous material be spandex, polypropylene, terylene,
Cellulose acetate fibre, polyacrylonitrile fibre or polyethylene.
Air clearance in described spinning process is moderate, has higher with the PVDF hollow-fibre membrane prepared by ensureing
Peel strength.
The preparation method of a kind of unpowered PVDF hollow-fibre membrane of the present invention, first carries out table by inorganic additive
Face is modified, to improve hydrophilicity, increases dispersibility in organic solvent, the most beneficially inorganic additive and PVDF
Affine, make the stronger fiber liner surface that is attached to of PVDF resin, and do not affect the excellent properties of PVDF itself.
Fiber bushing pipe of the present invention is functional fiber bushing pipe, uses the fibrous material of unlike material, controls fibrous material
Count, be prepared for the functional fibre bushing pipe with binding ability stronger with PVDF, by specific spinning technique,
PVDF casting solution is coated to functional fibre tube-surface, and more common reinforced pipe membrane material has higher peel strength,
Service life is long.
A kind of preparation method of the unpowered PVDF hollow-fibre membrane of the present invention, membrane material have preferable hydrophilicity and
Higher mechanical strength, preparation process is simple, easily realizes industrialized production, environment will not cause any pollution,
In actual wastewater treatment process, efficiency is high, simple to operate, it is possible to realize unpowered water outlet, and the service life of film is long,
Backwash process is simple, it is not necessary to cleaning agent, reduces production cost, has wide value and application prospect.
Accompanying drawing explanation
Fig. 1 is PVDF pure film contact angle figure；
Fig. 2 is contact angle figure after PVDF blending and modifying；
Fig. 3 is pvdf membrane material SEM before modification figure；
Fig. 4 is pvdf membrane material SEM after modification figure.
Detailed description of the invention
Detailed description of the invention one: in present embodiment, the preparation method of unpowered PVDF hollow-fibre membrane is in the steps below
Carry out:
Step one, the modification of inorganic additive: the kieselguhr that particle diameter is 500nm is added second by the amount that mass fraction is 5%
In alcoholic solution (volumetric concentration 15%), under the conditions of 50 DEG C of waters bath with thermostatic control, with 250r/min magnetic agitation 0.5h, then
Adding VTES in mixed liquor, wherein, kieselguhr with the mass ratio of VTES is
0.5:1, cools down water back flow reaction 3h, filters, and filtering residue ethanol solution washs 3 times, puts in vacuum drying oven, 60 DEG C
Vacuum drying 3h.
Step 2, PVDF casting solution configure: the modification infusorial earth that mass fraction is 0.5% is added N, N-dimethyl formyl
In amine solvent, under the conditions of 40 DEG C of waters bath with thermostatic control, with the frequency ultrasound vibration 0.5h of 10KHz, being subsequently adding mass fraction is
The PEG400 of 2%, under the conditions of 50 DEG C of waters bath with thermostatic control, mechanical agitation 2h, add PVDF powder, continue with 50 DEG C
Water bath with thermostatic control is heated, and mechanical agitation 6h is configured to casting solution.
Step 3, hollow-fibre membrane spinning: PVDF casting solution is poured into spinning-drawing machine material storage kettle tank and seals, add with 50 DEG C of constant temperature
Heat, is evacuated to 0.04MPa, standing and defoaming 4h with vacuum pump by system vacuum, is then filled with nitrogen to still tank, adjusts still
Pressure tank is 0.05MPa, and coagulation bath temperature is 30 DEG C, opens dosing pump, extrudes casting solution with 6mL/min speed, if
Determining air clearance is 0.1m, and functional fibre bushing pipe hub rotation speed is 6r/min, and wire winding speed is protected with functional fibre bushing pipe wheel hub
Holding consistent, casting solution is coated with through spinneret and is uniformly layed onto function liner surface.
Step 4, film forming procedure: from spinning head pull-out pvdf membrane aqueous phase coagulating bath through inversion of phases film-forming,
The membrane material prepared is cut off, is placed in Rinsing Area immersion 24h, at room temperature dries after taking-up.
Fig. 2, Fig. 1 show that PVDF rear pure water contact angle before modified is dropped to 68.64o by 81.59o, and hydrophilic is greatly improved,
Fig. 4, Fig. 3 illustrate that PVDF inorganic additive after modification is successfully loaded in PVDF, improve the surface knot of film
Structure.
Detailed description of the invention two: in present embodiment, the preparation method of unpowered PVDF hollow-fibre membrane is in the steps below
Carry out:
Step one, the modification of inorganic additive: the kieselguhr that particle diameter is 1000nm is added by the amount that mass fraction is 5%
In ethanol solution (volumetric concentration is 15%), under the conditions of 50 DEG C of waters bath with thermostatic control, with 280r/min magnetic agitation 0.5h, so
Adding VTES in backward mixed liquor, wherein, kieselguhr with the mass ratio of VTES is
0.5:1, cools down water back flow reaction 3h, filters, and filtering residue ethanol solution washs 3 times, puts in vacuum drying oven, 60 DEG C
Vacuum drying 3h.
Step 2, PVDF casting solution configure: the modification infusorial earth that mass fraction is 0.6% is added N, N-dimethyl formyl
In amine solvent, under the conditions of 60 DEG C of waters bath with thermostatic control, with the frequency ultrasound vibration 0.5h of 10KHz, being subsequently adding mass fraction is
The Macrogol 600 of 2%, under the conditions of 60 DEG C of waters bath with thermostatic control, mechanical agitation 2h, add PVDF powder, continue with 60 DEG C
Water bath with thermostatic control is heated, and mechanical agitation 6h is configured to casting solution.
Step 3, hollow-fibre membrane spinning: PVDF casting solution is poured into spinning-drawing machine material storage kettle tank and seals, add with 60 DEG C of constant temperature
Heat, is evacuated to 0.04MPa, standing and defoaming 4h with vacuum pump by system vacuum, is then filled with nitrogen to still tank, adjusts still
Pressure tank is 0.05MPa, and coagulation bath temperature is 30 DEG C, opens dosing pump, extrudes casting solution with 7mL/min speed, if
Determining air clearance is 0.2m, and functional fibre bushing pipe hub rotation speed is 6r/min, and wire winding speed is protected with functional fibre bushing pipe wheel hub
Holding consistent, casting solution is coated with through spinneret and is uniformly layed onto function liner surface.
Step 4, film forming procedure: from spinning head pull-out pvdf membrane aqueous phase coagulating bath through inversion of phases film-forming,
The membrane material prepared is cut off, is placed in Rinsing Area immersion 24h, at room temperature dries after taking-up.
Unpowered PVDF hollow-fibre membrane prepared by present embodiment and pure water contact angle are 71.32 °.
Detailed description of the invention three: in present embodiment, the preparation method of unpowered PVDF hollow-fibre membrane is in the steps below
Carry out:
Step one, the modification of inorganic additive: the silicon dioxide that particle diameter is 500nm is added by the amount that mass fraction is 5%
In ethanol solution (volumetric concentration is 15%), under the conditions of 50 DEG C of waters bath with thermostatic control, with 250r/min magnetic agitation 0.5h, so
Backward mixed liquor adds vinyl three ('beta '-methoxy ethyoxyl) silane, wherein, silicon dioxide and vinyl three (β-
Methoxy ethoxy) mass ratio of silane is 0.5:1, cools down water back flow reaction 3h, filters, filtering residue ethanol solution washs
3 times, put in vacuum drying oven, 60 DEG C of vacuum drying 3h.
Step 2, PVDF casting solution configure: the improved silica that mass fraction is 0.5% is added N, N-dimethyl methyl
In amide solvent, under the conditions of 40 DEG C of waters bath with thermostatic control, with the frequency ultrasound vibration 0.5h of 10KHz, it is subsequently adding mass fraction
Be the PEG400 of 2%, under the conditions of 50 DEG C of waters bath with thermostatic control, mechanical agitation 2h, add PVDF powder, continue with
50 DEG C of water bath with thermostatic control heating, mechanical agitation 6h, it is configured to casting solution.
Step 3, hollow-fibre membrane spinning: PVDF casting solution is poured into spinning-drawing machine material storage kettle tank and seals, add with 50 DEG C of constant temperature
Heat, is evacuated to 0.04MPa, standing and defoaming 4h with vacuum pump by system vacuum, is then filled with nitrogen to still tank, adjusts still
Pressure tank is 0.05MPa, and coagulation bath temperature is 30 DEG C, opens dosing pump, extrudes casting solution with 6mL/min speed, if
Determining air clearance is 0.1m, and functional fibre bushing pipe hub rotation speed is 6r/min, and wire winding speed is protected with functional fibre bushing pipe wheel hub
Holding consistent, casting solution is coated with through spinneret and is uniformly layed onto function liner surface.
Step 4, film forming procedure: from spinning head pull-out pvdf membrane aqueous phase coagulating bath through inversion of phases film-forming,
The membrane material prepared is cut off, is placed in Rinsing Area immersion 24h, at room temperature dries after taking-up.
Unpowered PVDF hollow-fibre membrane prepared by present embodiment and pure water contact angle are 59.78 °.
Detailed description of the invention four: in present embodiment, the preparation method of unpowered PVDF hollow-fibre membrane is in the steps below
Carry out:
Step one, the modification of inorganic additive: being 500nm silicon dioxide by particle diameter adds second by the amount that mass fraction is 5%
In alcoholic solution (volumetric concentration is 25%), under the conditions of 50 DEG C of waters bath with thermostatic control, with 270r/min magnetic agitation 0.5h, then
Vinyl three ('beta '-methoxy ethyoxyl) silane, wherein, silicon dioxide and vinyl three (beta-methoxy is added in mixed liquor
Base oxethyl) mass ratio of silane is 0.5:1, cools down water back flow reaction 3.5h, filters, filtering residue ethanol solution washs 3
Secondary, put in vacuum drying oven, 60 DEG C of vacuum drying 3h.
Step 2, PVDF casting solution configure: the improved silica that mass fraction is 1% is added N, N-dimethyl methyl
In amide solvent, under the conditions of 40 DEG C of waters bath with thermostatic control, with the frequency ultrasound vibration 0.5h of 10KHz, it is subsequently adding mass fraction
It is the PEG400 of 2.5%, under the conditions of 60 DEG C of waters bath with thermostatic control, mechanical agitation 2h, add PVDF powder, continue
With 60 DEG C of water bath with thermostatic control heating, mechanical agitation 6h, it is configured to casting solution.Step 3, hollow-fibre membrane spinning: by PVDF
Casting solution is poured spinning-drawing machine material storage kettle tank into and seals, and with 60 DEG C of heated at constant temperature, system vacuum is evacuated to vacuum pump
0.04MPa, standing and defoaming 4h, then it is filled with nitrogen to still tank, adjusting still pressure tank is 0.05MPa, and coagulation bath temperature is
35 DEG C, opening dosing pump, extrude casting solution with 8mL/min speed, setting air spacing is 0.5m, functional fibre bushing pipe
Hub rotation speed is 6r/min, and wire winding speed keeps consistent with functional fibre bushing pipe wheel hub, and casting solution is coated with through spinneret and is uniformly layed onto
Function liner surface.
Step 4, film forming procedure: from spinning head pull-out pvdf membrane aqueous phase coagulating bath through inversion of phases film-forming,
The membrane material prepared is cut off, is placed in Rinsing Area immersion 24h, at room temperature dries after taking-up.
Unpowered PVDF hollow-fibre membrane prepared by present embodiment and pure water contact angle are 74.39 °.
Detailed description of the invention five: in present embodiment, the preparation method of unpowered PVDF hollow-fibre membrane is in the steps below
Carry out:
Step one, the modification of inorganic additive: the Kaolin that particle diameter is 3000nm is added by the amount that mass fraction is 5%
In ethanol solution (volumetric concentration is 40%), under the conditions of 50 DEG C of waters bath with thermostatic control, with 270r/min magnetic agitation 0.5h, so
Backward mixed liquor adds vinyl three ('beta '-methoxy ethyoxyl) silane, wherein, Kaolin and vinyl three (beta-methoxy
Base oxethyl) mass ratio of silane is 0.5:1, cools down water back flow reaction 3.5h, filters, filtering residue ethanol solution washs 3
Secondary, put in vacuum drying oven, 60 DEG C of vacuum drying 3h.
Step 2, PVDF casting solution configure: the modified kaolin that mass fraction is 1% is added N,N-dimethylformamide
In solvent, under the conditions of 40 DEG C of waters bath with thermostatic control, with the frequency ultrasound vibration 0.5h of 10KHz, being subsequently adding mass fraction is 2.5%
PEG20000, under the conditions of 60 DEG C of waters bath with thermostatic control, mechanical agitation 2h, add PVDF powder, continue with 60 DEG C
Water bath with thermostatic control is heated, and mechanical agitation 6h is configured to casting solution.
Step 3, hollow-fibre membrane spinning: PVDF casting solution is poured into spinning-drawing machine material storage kettle tank and seals, with 60 DEG C of perseverances
Temperature heating, is evacuated to 0.04MPa, standing and defoaming 4h with vacuum pump by system vacuum, is then filled with nitrogen to still tank, adjusts
Whole still pressure tank is 0.05MPa, and coagulation bath temperature is 35 DEG C, opens dosing pump, extrudes casting solution with 8mL/min speed,
Setting air spacing is 0.5m, and functional fibre bushing pipe hub rotation speed is 6r/min, wire winding speed and functional fibre bushing pipe wheel hub
Keeping consistent, casting solution is coated with through spinneret and is uniformly layed onto function liner surface.
Step 4, film forming procedure: from spinning head pull-out pvdf membrane aqueous phase coagulating bath through inversion of phases film-forming,
The membrane material prepared is cut off, is placed in Rinsing Area immersion 24h, at room temperature dries after taking-up.
Unpowered PVDF hollow-fibre membrane prepared by present embodiment and pure water contact angle are 66.51 °.
Detailed description of the invention six: in present embodiment, the preparation method of unpowered PVDF hollow-fibre membrane is in the steps below
Carry out:
Step one, the modification of inorganic additive: the Kaolin that particle diameter is 3000nm is added by the amount that mass fraction is 5%
In ethanol solution (volumetric concentration is 40%), under the conditions of 50 DEG C of waters bath with thermostatic control, with 250r/min magnetic agitation 0.5h, so
Adding VTES in backward mixed liquor, wherein, Kaolin with the mass ratio of VTES is
0.5:1, cools down water back flow reaction 3h, filters, and filtering residue ethanol solution washs 3 times, puts in vacuum drying oven, 60 DEG C
Vacuum drying 3h.
Step 2, PVDF casting solution configure: the modified kaolin that mass fraction is 0.5% is added N, N-dimethyl formyl
In amine solvent, under the conditions of 40 DEG C of waters bath with thermostatic control, with the frequency ultrasound vibration 0.5h of 10KHz, being subsequently adding mass fraction is
The PEG400 of 2%, under the conditions of 50 DEG C of waters bath with thermostatic control, mechanical agitation 2h, add PVDF powder, continue with 50 DEG C
Water bath with thermostatic control is heated, and mechanical agitation 6h is configured to casting solution.
Step 3, hollow-fibre membrane spinning: PVDF casting solution is poured into spinning-drawing machine material storage kettle tank and seals, add with 50 DEG C of constant temperature
Heat, is evacuated to 0.04MPa, standing and defoaming 4h with vacuum pump by system vacuum, is then filled with nitrogen to still tank, adjusts still
Pressure tank is 0.05MPa, and coagulation bath temperature is 30 DEG C, opens dosing pump, extrudes casting solution with 6mL/min speed, if
Determining air clearance is 0.1m, and functional fibre bushing pipe hub rotation speed is 6r/min, and wire winding speed is protected with functional fibre bushing pipe wheel hub
Holding consistent, casting solution is coated with through spinneret and is uniformly layed onto function liner surface.
Step 4, film forming procedure: from spinning head pull-out pvdf membrane aqueous phase coagulating bath through inversion of phases film-forming,
The membrane material prepared is cut off, is placed in Rinsing Area immersion 24h, at room temperature dries after taking-up.
Unpowered PVDF hollow-fibre membrane prepared by present embodiment and pure water contact angle are 65.72 °.
Claims (10)
1. the preparation method of a unpowered PVDF hollow-fibre membrane, it is characterised in that this preparation method is carried out in the steps below:
Step one, inorganic additive is added in ethanol solution, stir with (250～350) r/min magnetic force under (50～80) DEG C water bath with thermostatic control
Mixing (0.5～1) h, add coupling agent, cool down water back flow reaction (3～5) h, filter, filtering residue ethanol solution washing (3～5) is secondary,
(3～5) h it is vacuum dried under the conditions of 60～90 DEG C.
Step 2, step one is processed after inorganic additive add in organic solvent, under the conditions of (40～70) DEG C water bath with thermostatic control, with (10～
40) frequency ultrasound vibration (0.5～2) h of KHz, is subsequently adding porogen, then under the conditions of (50～90) DEG C water bath with thermostatic control, machinery stirs
Mix (2～6) h, add PVDF powder, continue to heat in (50～90 DEG C) water bath with thermostatic control, mechanical agitation (6～13) h, cast
Film liquid；
Casting solution is poured into the material storage kettle tank of spinning-drawing machine and seals by step 3, under the conditions of (50～90) DEG C heated at constant temperature, with vacuum pump by system
Vacuum is evacuated to 0.04～0.1MPa, standing and defoaming 4～8h, is then filled with nitrogen to material storage kettle tank, adjust material storage kettle pressure tank be 0.05～
0.3MPa, coagulation bath temperature is 30～50 DEG C, opens dosing pump, extrudes casting solution with (6～16) mL/min speed, and setting air spacing is
(0.1～0.5) m, functional fibre bushing pipe hub rotation speed is (6～12) r/min, and wire winding speed keeps consistent with functional fibre bushing pipe wheel hub, casting film
Liquid through spinneret be coated with uniformly be layed onto function liner surface, in coagulating bath through inversion of phases film-forming, the membrane material prepared is cut off, place
In Rinsing Area, soak (24～36) h, at room temperature dry after taking-up.
The preparation method of a kind of unpowered PVDF hollow-fibre membrane the most according to claim 1, it is characterised in that inorganic in step one add
The mass ratio adding agent and coupling agent is (0.5～1): 1.
The preparation method of a kind of unpowered PVDF hollow-fibre membrane the most according to claim 1, it is characterised in that inorganic described in step one
Additive is kieselguhr, silicon dioxide, Kaolin, alchlor, calcium carbonate, titanium dioxide or clay.
The preparation method of a kind of unpowered PVDF hollow-fibre membrane the most according to claim 1, it is characterised in that inorganic described in step one
The particle diameter of additive is 500～3000nm.
The preparation method of a kind of unpowered PVDF hollow-fibre membrane the most according to claim 1, it is characterised in that inorganic described in step one
Additive mass fraction in ethanol solution is 5%～15%.
The preparation method of a kind of unpowered PVDF hollow-fibre membrane the most according to claim 1, it is characterised in that coupling described in step one
Agent is VTES, vinyl three ('beta '-methoxy ethyoxyl) silane, γ-aminopropyltrimethoxysilane, isopropyl three (two
Octyl group pyrophosphoric acid acyloxy) titanate esters, isopropyl two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) titanate esters, monoalkoxy insatiable hunger or fat
Acid titanate esters.
The preparation method of a kind of unpowered PVDF hollow-fibre membrane the most according to claim 1, it is characterised in that organic described in step 2
Solvent is DMF, N,N-dimethylacetamide, dimethyl sulfoxide or N-Methyl pyrrolidone, the interpolation after step one process
Agent mass fraction in casting solution is 0.5%～5%.
The preparation method of a kind of unpowered PVDF hollow-fibre membrane the most according to claim 1, it is characterised in that pore described in step 2
Agent is PEG400, Macrogol 600, PEG20000, PVP K30, lithium chloride or sodium chloride, additive matter
Amount is the 2%～8% of casting solution gross mass.
The preparation method of a kind of unpowered PVDF hollow-fibre membrane the most according to claim 1, it is characterised in that step 2 is at casting solution
In PVDF mass fraction be 13%～19%.
The preparation method of a kind of unpowered PVDF hollow-fibre membrane the most according to claim 1, it is characterised in that function described in step 3
Fiber bushing pipe is to be formed by different fibrous material braidings, and fibrous material is spandex, polypropylene, terylene, cellulose acetate fibre, polyacrylonitrile fibre
Or polyethylene.
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| CN107913603A (en) * | 2017-10-09 | 2018-04-17 | 李亮 | Woven tube enhancement type hollow fiber film and its preparation facilities and production technology |
| CN108187509A (en) * | 2018-01-25 | 2018-06-22 | 天津大学 | A kind of cobaltous ferrocyanide PVDF hollow-fibre membranes, preparation method and its usage |
| CN108499375A (en) * | 2018-01-25 | 2018-09-07 | 天津大学 | A kind of preparation method of big flux cobaltous ferrocyanide PVDF flat composite membranes |
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