CN107096396A - A kind of polyvinylidene fluoride hollow fiber miillpore filter and preparation method thereof - Google Patents
A kind of polyvinylidene fluoride hollow fiber miillpore filter and preparation method thereof Download PDFInfo
- Publication number
- CN107096396A CN107096396A CN201710354891.4A CN201710354891A CN107096396A CN 107096396 A CN107096396 A CN 107096396A CN 201710354891 A CN201710354891 A CN 201710354891A CN 107096396 A CN107096396 A CN 107096396A
- Authority
- CN
- China
- Prior art keywords
- solvent
- preparation
- liquid
- hollow fiber
- core liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
- B01D67/0002—Organic membrane manufacture
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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
Abstract
The invention discloses a kind of preparation method of polyvinylidene fluoride hollow fiber miillpore filter, specific steps include：The preparation of casting solution；The preparation of core liquid；Outer solidification liquid is prepared；Spinning；Rinsing displacement；Heat treatment.The present invention prepares PVDF doughnut miillpore filters using Thermal inactive with the method that solution phase inversion is combined, and compared with solution phase inversion, eliminates finger-like pore, the microstructure of film is more reasonable；Compared with thermally induced phase separation, operation is simplified, without solvent extraction, cost is reduced；The inorganic additive such as Nano glass powder or nanometer silicon carbide is added in formula of casting, the intensity of film silk is added, the pressure-resistant and anti-wear performance of film silk is in particular improved；The film silk of internal pressure or external pressure with cortex can be prepared as needed, and subcortex microstructure is also network-like structure or granulation mass cumuliformis structure, and gained film silk separating property is good, and flux is big.
Description
Technical field
The invention belongs to water process technology field of membrane materials, and in particular to a kind of polyvinylidene fluoride hollow fiber micropore filter
Film and preparation method thereof.
Background technology
Kynoar（PVDF）With good heat endurance and chemical stability, the weatherability of protrusion and resistance to ag(e)ing
And good mechanical performance, therefore PVDF doughnuts miillpore filter obtains in separation industries especially sewage treatment industry
It is widely applied.
It is higher to the flux, antifouling property and intensity requirement of film for the PVDF hollow fiber filter membranes of sewage disposal.
Membrane flux and antifouling property are relevant with the hydrophilicity of film, generally increase the parent of film by the way of blending and modifying
It is aqueous.Patent CN200710110891.6, CN200710178460.3, CN200810243108.8,
CN201110383379.5, CN201210348071.1, CN201210401611.8, CN201310492612.2 etc. are disclosed
About the method by the way that the hydrophily and antifouling property that improve pvdf membrane is blended.Patent CN201410202695.1 is then by embedding
Section polymer carries out hydrophilic modifying to film, and patent CN201410854869.2 improves the hydrophily of film by graft modification.
On the raising of film-strength, there are three kinds of thinkings, one kind is to increase one or a few fiber in film silk, and it is so-called to be formed
" concrete formula film ", Chinese patent CN200510013255.2, CN201010209047.0, CN201110119197.7,
CN201110243287.7, CN201410007868.4, CN201410423395.6, CN201510175832.1,
CN201510425431.7 etc. discloses similar use filament to the enhanced method of film strength.By this method it is enhanced in
Hollow fiber film, axially can only play booster action, in the radial direction of film, any booster action not had at all.It is another hollow
The enhanced method of tunica fibrosa is, by the outside film in woven tube, to form the composite membrane with supporting layer, Chinese patent
CN200910097143.8, CN201110411620.0, CN201210280967.0, CN201310395624.3,
CN201510254916.4, CN201610472418.1, CN201610466248.6, CN201610680345.5 etc. are used should
Thinking strengthens hollow-fibre membrane.The key of this method is how to increase affine between film layer and support braid
Power, prevents film layer from peeling off in use.The method of the third increase doughnut film-strength, is to want to do in itself from film layer
Method, the intensity of increase film silk.
The content of the invention
It is an object of the invention to provide a kind of polyvinylidene fluoride hollow fiber miillpore filter for sewage disposal and its
Preparation method, the polyvinylidene fluoride hollow fiber miillpore filter intensity obtained using this method is high, and water flux is big, antifouling property
It is good, and process is simple.
The purpose of the present invention is realized in the following manner：
A kind of preparation method of polyvinylidene fluoride hollow fiber miillpore filter, is comprised the following steps that：
（1）The preparation of casting solution：By PVDF resins, solvents, casting solution non-solvent, hydrophilic modifier, inorganic additive
In mass ratio 1:（1.6-3.0）:（0.02-0.4）:（0.01-0.2）:（0-0.1）Ratio be added in stirred tank, in temperature
128-186 DEG C of heating for dissolving, standing and defoaming 4-6 hours forms casting solution；
（2）The preparation of core liquid：By core liquid solvent, core liquid non-solvent and water in mass ratio 1:（0.5-2.0）:（0-0.1）Ratio
It is added in core flow container, stirs at room temperature, obtains interior solidification core liquid；
（3）Outer solidification liquid is prepared：By outer solidification liquid solvent, outer solidification liquid non-solvent and water in mass ratio 1:（0.5-2.0）:（0-
0.1）Ratio be added in coagulating tank, stir at room temperature, obtain outer solidification liquid；
（4）Spinning：By step（1）The casting solution of preparation is squeezed into spinning head, while being passed through step（2）The core liquid of preparation, control
The range of flow of casting solution processed is 8-40ml/min, and the range of flow of core liquid is 3-15ml/min, casting solution is passed through spinning head
Afterwards, form the hollow form fiber of certain specification size, by 5-50mm dry journey distance with after air exchange, into coagulating tank
In directly contacted with outer solidification liquid, while cooling, carry out solvent-nonsolvent exchange split-phase solidification, formed have it is porous
Hollow-fibre membrane silk, the hollow fiber film thread come out from coagulating bath winds through driving wheel, leaves coagulating tank；
（5）Rinsing displacement：Hollow-fibre membrane silk wound through driving wheel after enter potcher, with potcher built with hot water it is straight
Contact, in carrying out online rinsing processing at 30-60 DEG C, makes the solvent in film silk fully be exchanged with pure water, is put through rinsing
After changing, film silk is wound on wire drawing wheel；
（6）Heat treatment：Hollow-fibre membrane silk on wire drawing wheel is subjected to Length-fixing cutting, and uses pure water rinsed clean
Afterwards, film silk two ends are fixed, be put into heat treatment groove, in carrying out drawing and setting processing at 60-90 DEG C, stretch ratio is no more than
130%, drawn heat treatment 0.5-2 hours.
The step（1）In solvents for triethyl phosphate or trimethyl phosphate and ethylene glycol ether acetate or
Propylene-glycol ethyl ether acetate is 1 in mass ratio:（0.1-1）The mixed solvent mixed.
The step（1）In casting solution non-solvent, step（2）In core liquid non-solvent and step（3）In outer solidification
Liquid non-solvent is at least one of glycerine, propane diols, ethylene glycol, diethylene glycol or triethylene glycol.
The step（1）In hydrophilic modifier be polyvinyl acetate or polyvinylpyrrolidone.
The step（1）In inorganic additive at least one of for nano-glass, nanometer silicon carbide.
The step（2）In core liquid solvent and step（3）In outer solidification liquid solvent be triethyl phosphate or phosphoric acid
Trimethyl, or be that triethyl phosphate or trimethyl phosphate press quality with ethylene glycol ether acetate or propylene-glycol ethyl ether acetate
Than for 1:（0.1-1）The mixed solvent mixed.
When spinned be outer press mold when, the step（3）In outer solidification liquid in add outer solidification liquid gross mass
0.1-1% water.
The step（4）In spinneret temperature be 100-130 DEG C, from stirred tank to spinning head formed natural temperature ladder
Degree, core liquid temperature control is between 10-35 DEG C, and coagulation bath temperature is controlled between 5-35 DEG C, and spinning speed is controlled in 5-25m/
Between min.
When spinned be interior press mold when, the step（2）In core liquid in add core liquid gross mass 0.1-1% water.
The hollow fibre of Kynoar prepared according to the preparation method of above-mentioned polyvinylidene fluoride hollow fiber miillpore filter
Tie up miillpore filter.
Relative to prior art, the advantage of the invention is that：
1）The present invention prepares PVDF doughnut miillpore filters using Thermal inactive with the method that solution phase inversion is combined,
Compared with solution phase inversion, finger-like pore is eliminated, the microstructure of film is more reasonable；Compared with thermally induced phase separation, simplify
Operation, without solvent extraction, reduces cost；
2）The doughnut miillpore filter prepared using dicyandiamide solution of the present invention and method, film layer microstructure is network
Shape structure or granulation mass cumuliformis structure, percent opening are high, and membrane flux is big；
3）Mixed solvent has been used in formula of casting, by adjusting mixed proportion, the viscosity of casting solution can have been changed and can be spun
Property, improve product quality；
4）Non-solvent has been used in formula of casting, casting solution split-phase speed and PVDF crystalline states has been changed, promotes to be formed
Crystal grain heaped-up sponge hole, occurs without finger-like pore, and the hollow-fibre membrane duct formed is uniform, and porosity is high, can be significantly
Improve the permeant flux of product；
5）The inorganic additive such as Nano glass powder or nanometer silicon carbide is added in formula of casting, the intensity of film silk is added,
In particular improve the pressure-resistant and anti-wear performance of film silk；
6）Can prepare as needed internal pressure or external pressure with cortex film silk, subcortex microstructure be also network-like structure or
Grain heaped-up structure, gained film silk separating property is good, and flux is big；
7）Film silk will not shrink, the assembly property being made is more stable again in use after Overheating Treatment.
Embodiment
Embodiment 1：
A kind of preparation method of polyvinylidene fluoride hollow fiber miillpore filter, is comprised the following steps that：
（1）The preparation of casting solution：By PVDF resins, solvents, casting solution non-solvent, hydrophilic modifier, inorganic additive
In mass ratio 1:（1.6-3.0）:（0.02-0.4）:（0.01-0.2）:（0-0.1）Ratio be added in stirred tank, in temperature
128-186 DEG C of heating for dissolving, standing and defoaming 4-6 hours forms casting solution；
（2）The preparation of core liquid：By core liquid solvent, core liquid non-solvent and water in mass ratio 1:（0.5-2.0）:（0-0.1）Ratio
It is added in core flow container, stirs at room temperature, obtains interior solidification core liquid；
（3）Outer solidification liquid is prepared：By outer solidification liquid solvent, outer solidification liquid non-solvent and water in mass ratio 1:（0.5-2.0）:（0-
0.1）Ratio be added in coagulating tank, stir at room temperature, obtain outer solidification liquid；
（4）Spinning：By step（1）The casting solution of preparation is squeezed into spinning head, while being passed through step（2）The core liquid of preparation, control
The range of flow of casting solution processed is 8-40ml/min, and the range of flow of core liquid is 3-15ml/min, casting solution is passed through spinning head
Afterwards, form the hollow form fiber of certain specification size, by 5-50mm dry journey distance with after air exchange, into coagulating tank
In directly contacted with outer solidification liquid, while cooling, carry out solvent-nonsolvent exchange split-phase solidification, formed have it is porous
Hollow-fibre membrane silk, the hollow fiber film thread come out from coagulating bath winds through driving wheel, leaves coagulating tank, spinning speed
Depending on the rotating speed of driving wheel；
（5）Rinsing displacement：Hollow-fibre membrane silk wound through driving wheel after enter potcher, with potcher built with hot water it is straight
Contact, in carrying out online rinsing processing at 30-60 DEG C, makes the solvent in film silk fully be exchanged with pure water, is put through rinsing
After changing, film silk is wound on wire drawing wheel；
（6）Heat treatment：Hollow-fibre membrane silk on wire drawing wheel is subjected to Length-fixing cutting, and uses pure water rinsed clean
Afterwards, film silk two ends are fixed, be put into heat treatment groove, in carrying out drawing and setting processing at 60-90 DEG C, stretch ratio is no more than
130%, drawn heat treatment is after 0.5-2 hours, and film silk outward appearance is straight, is convenient for encapsulation process, while the film that encapsulation is finished
Film silk shrinkage phenomenon will not occur again in use for component.
Step（1）In solvents be triethyl phosphate or trimethyl phosphate and ethylene glycol ether acetate or the third two
Alcohol ethyl ether acetate ester is 1 in mass ratio:（0.1-1）The mixed solvent mixed.It can not change solid using mixed solvent
In the case of body material rate, by adjusting the mixed proportion of different solvents, change the viscosity and spinnability of casting solution, so as to carry
High yield quality.
Step（1）In casting solution non-solvent, step（2）In core liquid non-solvent and step（3）In outer solidification liquid it is non-
Solvent is at least one of glycerine, propane diols, ethylene glycol, diethylene glycol or triethylene glycol.Step（1）In casting solution it is non-
Solvent, step（2）In core liquid non-solvent and step（3）In outer solidification liquid non-solvent be that higher boiling small molecule is organic molten
Agent, the higher boiling Small molecule organic solvents are material of preparing（PVDF）Poor solvent, its presence causes casting solution unstable,
Promote casting solution split-phase and influence PVDF crystalline states, form crystal grain heaped-up sponge hole, occur without finger-like pore, formed
Hollow-fibre membrane duct is uniform, and porosity is high, is greatly improved the permeant flux of product.
Step（1）In hydrophilic modifier be polyvinyl acetate or polyvinylpyrrolidone.Hydrophilic modifier can be carried
The hydrophilicity of high PVDF hollow-fibre membranes, improves permeant flux.
Step（1）In inorganic additive at least one of for nano-glass, nanometer silicon carbide.Inorganic additive is uniform
Ground is dispersed in casting solution, as nucleus in phase process, makes PVDF rapid crystallizations, it is to avoid form bulky grain crystal, so that
Improve the microstructure of film, improve the friction resistant and compressive property of film silk, effectively improve film silk service life.
Step（2）In core liquid solvent and step（3）In outer solidification liquid solvent be triethyl phosphate or tripotassium phosphate
Ester, or be that triethyl phosphate or trimethyl phosphate are in mass ratio with ethylene glycol ether acetate or propylene-glycol ethyl ether acetate
1:（0.1-1）The mixed solvent mixed.
When spinned be outer press mold when, the step（3）In outer solidification liquid in add outer solidification liquid gross mass
0.1-1% water, can form dense layer surface in the outer surface of film silk in spinning process, by control outer solidification liquid reclaimed water number,
Control the compactness extent of cortex；When spinned be interior press mold when, do not add water in outer solidification liquid, film outer surface dense skin can be prevented
Layer occurs.
Step（4）In spinneret temperature be 100-130 DEG C, from stirred tank to spinning head formed natural temperature gradient, core
Liquid temperature control between 10-35 DEG C, coagulation bath temperature control between 5-35 DEG C, spinning speed control 5-25m/min it
Between.
When spinned be interior press mold when, the step（2）In core liquid in add core liquid gross mass 0.1-1% water,
Can in spinning process film silk inner surface formation dense layer surface, by control core liquid reclaimed water number, control cortex densification
Degree；When spinned be outer press mold when, do not add water in core liquid, can prevent film inner surface dense layer surface from occurring.
The hollow fibre of Kynoar prepared according to the preparation method of above-mentioned polyvinylidene fluoride hollow fiber miillpore filter
Tie up miillpore filter.
Embodiment 2：
A kind of preparation method of polyvinylidene fluoride hollow fiber miillpore filter, is comprised the following steps that：
（1）The preparation of casting solution：By PVDF resins 100g, solvents 160g, glycerine 2g, polyvinyl acetate 1g by certain
Order is added in stirred tank, and in 128 DEG C of heating for dissolving of temperature, standing and defoaming 4 hours forms casting solution；
（2）The preparation of core liquid：Triethyl phosphate 100g, glycerine 50g are added in core flow container, stirs, obtains at room temperature
To interior solidification core liquid；
（3）Outer solidification liquid is prepared：Triethyl phosphate 100g, glycerine 50g are added in coagulating tank, stir equal at room temperature
It is even, obtain outer solidification liquid；
（4）Spinning：By step（1）The casting solution of preparation is squeezed into spinning head, and spinneret temperature is 100 DEG C, from stirred tank to
Spinning head formation natural temperature gradient, while being passed through step（2）The core liquid of preparation, core liquid temperature control is between 10 DEG C, control
The range of flow of casting solution is 8ml/min, and the range of flow of core liquid is 3ml/min, after making casting solution by spinning head, forms one
Determine the hollow form fiber of specification, by 5mm dry journey distance with after air exchange, into coagulating tank with outer solidification liquid
Directly contact, coagulation bath temperature is controlled between 5 DEG C, while cooling, carry out solvent-nonsolvent and exchange split-phase solidification,
Formed with porous hollow-fibre membrane silk, the hollow fiber film thread come out from coagulating bath is wound through driving wheel, leaves solidification
Bath, spinning speed is controlled between 5m/min；
（5）Rinsing displacement：Hollow-fibre membrane silk wound through driving wheel after enter potcher, with potcher built with hot water it is straight
Contact, in carrying out online rinsing processing at 30 DEG C, makes the solvent in film silk fully be exchanged with pure water, is replaced through rinsing
Afterwards, film silk is wound on wire drawing wheel；
（6）Heat treatment：Hollow-fibre membrane silk on wire drawing wheel is subjected to Length-fixing cutting, and uses pure water rinsed clean
Afterwards, film silk two ends are fixed, are put into heat treatment groove, in carrying out drawing and setting processing at 60 DEG C, stretch ratio is no more than 130%,
After drawn heat treatment 0.5 hour, film silk outward appearance is straight, is convenient for encapsulation process, while the membrane module that encapsulation is finished exists
Will not occur film silk shrinkage phenomenon during use again.
Step（1）In solvents mix for triethyl phosphate 145g and ethylene glycol ether acetate 15g
Mixed solvent.
Step（1）In casting solution non-solvent, step（2）In core liquid non-solvent and step（3）In outer solidification liquid it is non-
Solvent is glycerine.
Other be the same as Examples 1.
After tested, the fracture strength of gained polyvinylidene fluoride hollow fiber miillpore filter is 168MPa, and elongation at break is
310%, pure water flux 1988LMH@0.1MPa.
Embodiment 3：
A kind of preparation method of polyvinylidene fluoride hollow fiber miillpore filter, is comprised the following steps that：
（1）The preparation of casting solution：By PVDF resins 100g, solvents 180g, propane diols 5g, polyvinyl acetate 5g, receive
Rice glass 1g is added in stirred tank in certain sequence, and in 130 DEG C of heating for dissolving of temperature, standing and defoaming 5 hours forms casting film
Liquid；
（2）The preparation of core liquid：Triethyl phosphate 100g, propane diols 80g, water 1g are added in core flow container, stirred at room temperature
Uniformly, interior solidification core liquid is obtained；
（3）Outer solidification liquid is prepared：Triethyl phosphate 100g, propane diols 80g, water 1g are added in coagulating tank, at room temperature
Stir, obtain outer solidification liquid；
（4）Spinning：By step（1）The casting solution of preparation is squeezed into spinning head, and spinneret temperature is 105 DEG C, from stirred tank to
Spinning head formation natural temperature gradient, while being passed through step（2）The core liquid of preparation, core liquid temperature control is between 12 DEG C, control
The range of flow of casting solution is 10ml/min, and the range of flow of core liquid is 5ml/min, after making casting solution by spinning head, is formed
The hollow form fiber of certain specification size, by 10mm dry journey distance with after air exchange, being coagulated into coagulating tank with outer
Solid-liquid is directly contacted, and coagulation bath temperature is controlled between 10 DEG C, while cooling, is carried out solvent-nonsolvent and is exchanged split-phase
Solidification, is formed with porous hollow-fibre membrane silk, the hollow fiber film thread come out from coagulating bath winds through driving wheel, left
Coagulating tank, spinning speed is controlled between 8m/min；
（5）Rinsing displacement：Hollow-fibre membrane silk wound through driving wheel after enter potcher, with potcher built with hot water it is straight
Contact, in carrying out online rinsing processing at 35 DEG C, makes the solvent in film silk fully be exchanged with pure water, is replaced through rinsing
Afterwards, film silk is wound on wire drawing wheel；
（6）Heat treatment：Hollow-fibre membrane silk on wire drawing wheel is subjected to Length-fixing cutting, and uses pure water rinsed clean
Afterwards, film silk two ends are fixed, are put into heat treatment groove, in carrying out drawing and setting processing at 65 DEG C, stretch ratio is no more than 130%,
After drawn heat treatment 0.8 hour, film silk outward appearance is straight, is convenient for encapsulation process, while the membrane module that encapsulation is finished exists
Will not occur film silk shrinkage phenomenon during use again.
Step（1）In solvents mix for triethyl phosphate 150g and ethylene glycol ether acetate 30g
Mixed solvent.
Other be the same as Examples 1.
After tested, the fracture strength of gained polyvinylidene fluoride hollow fiber miillpore filter is 163MPa, and elongation at break is
300%, pure water flux 1842LMH@0.1MPa.
Embodiment 4：
（2）The preparation of core liquid：Triethyl phosphate 100g, propane diols 80g, water 0.18g are added in core flow container, stirred at room temperature
Mix uniform, obtain interior solidification core liquid；
（3）Outer solidification liquid is prepared：Triethyl phosphate 100g, propane diols 80g, water 0.18g are added in coagulating tank, in room temperature
Under stir, obtain outer solidification liquid；Other be the same as Examples 3.
Embodiment 5：
（2）The preparation of core liquid：Triethyl phosphate 100g, propane diols 80g, water 1.8g are added in core flow container, stirred at room temperature
Mix uniform, obtain interior solidification core liquid；
（3）Outer solidification liquid is prepared：Triethyl phosphate 100g, propane diols 80g, water 1.8g are added in coagulating tank, in room temperature
Under stir, obtain outer solidification liquid；Other be the same as Examples 3.
Embodiment 6：
A kind of preparation method of polyvinylidene fluoride hollow fiber miillpore filter, is comprised the following steps that：
（1）The preparation of casting solution：By PVDF resins 100g, solvents 200g, casting solution non-solvent 10g, polyvinyl acetate
Ester 8g, nano-glass 2g are added in stirred tank in certain sequence, in 140 DEG C of heating for dissolving of temperature, standing and defoaming 6 hours, shape
Into casting solution；
（2）The preparation of core liquid：Trimethyl phosphate 100g, core liquid non-solvent 100g, water 2g are added in core flow container, at room temperature
Stir, obtain interior solidification core liquid；
（3）Outer solidification liquid is prepared：Trimethyl phosphate 100g, outer solidification liquid non-solvent 100g, water 2g are added in coagulating tank,
Stir at room temperature, obtain outer solidification liquid；
（4）Spinning：By step（1）The casting solution of preparation is squeezed into spinning head, and spinneret temperature is 110 DEG C, from stirred tank to
Spinning head formation natural temperature gradient, while being passed through step（2）The core liquid of preparation, core liquid temperature control is between 15 DEG C, control
The range of flow of casting solution is 15ml/min, and the range of flow of core liquid is 6ml/min, after making casting solution by spinning head, is formed
The hollow form fiber of certain specification size, by 15mm dry journey distance with after air exchange, being coagulated into coagulating tank with outer
Solid-liquid is directly contacted, and coagulation bath temperature is controlled between 15 DEG C, while cooling, is carried out solvent-nonsolvent and is exchanged split-phase
Solidification, is formed with porous hollow-fibre membrane silk, the hollow fiber film thread come out from coagulating bath winds through driving wheel, left
Coagulating tank, spinning speed is controlled between 10m/min；
（5）Rinsing displacement：Hollow-fibre membrane silk wound through driving wheel after enter potcher, with potcher built with hot water it is straight
Contact, in carrying out online rinsing processing at 40 DEG C, makes the solvent in film silk fully be exchanged with pure water, is replaced through rinsing
Afterwards, film silk is wound on wire drawing wheel；
（6）Heat treatment：Hollow-fibre membrane silk on wire drawing wheel is subjected to Length-fixing cutting, and uses pure water rinsed clean
Afterwards, film silk two ends are fixed, are put into heat treatment groove, in carrying out drawing and setting processing at 70 DEG C, stretch ratio is no more than 130%,
After drawn heat treatment 1 hour, film silk outward appearance is straight, is convenient for encapsulation process, while the membrane module that encapsulation is finished makes
Will not occur film silk shrinkage phenomenon again during.
Step（1）In solvents mix for trimethyl phosphate 154g and ethylene glycol ether acetate 46g
Mixed solvent.
Step（1）In casting solution non-solvent mix for ethylene glycol 5g and diethylene glycol 5g, step（2）In core liquid
Non-solvent is that ethylene glycol 50g and diethylene glycol 50g is mixed, step（3）In outer solidification liquid non-solvent be propane diols second two
Alcohol 50g and diethylene glycol 50g are mixed.
Other be the same as Examples 1.
After tested, the fracture strength of gained polyvinylidene fluoride hollow fiber miillpore filter is 154MPa, and elongation at break is
280%, pure water flux 1790LMH@0.1MPa.
Embodiment 7：
A kind of preparation method of polyvinylidene fluoride hollow fiber miillpore filter, is comprised the following steps that：
（1）The preparation of casting solution：By PVDF resins 100g, solvents 220g, casting solution non-solvent 15g, polyvinyl acetate
Ester 10g, nanometer silicon carbide 4g are added in stirred tank in certain sequence, and in temperature, 150 DEG C dissolve by heating, standing and defoaming 4 hours,
Form casting solution；
（2）The preparation of core liquid：Trimethyl phosphate 100g, core liquid non-solvent 120g, water 4g are added in core flow container, at room temperature
Stir, obtain interior solidification core liquid；
（3）Outer solidification liquid is prepared：Trimethyl phosphate 100g, outer solidification liquid non-solvent 120g, water 4g are added in coagulating tank,
Stir at room temperature, obtain outer solidification liquid；
（4）Spinning：By step（1）The casting solution of preparation is squeezed into spinning head, and spinneret temperature is 115 DEG C, from stirred tank to
Spinning head formation natural temperature gradient, while being passed through step（2）The core liquid of preparation, core liquid temperature control is between 20 DEG C, control
The range of flow of casting solution is 20ml/min, and the range of flow of core liquid is 7ml/min, after making casting solution by spinning head, is formed
The hollow form fiber of certain specification size, by 20mm dry journey distance with after air exchange, being coagulated into coagulating tank with outer
Solid-liquid is directly contacted, and coagulation bath temperature is controlled between 20 DEG C, while cooling, is carried out solvent-nonsolvent and is exchanged split-phase
Solidification, is formed with porous hollow-fibre membrane silk, the hollow fiber film thread come out from coagulating bath winds through driving wheel, left
Coagulating tank, spinning speed is controlled between 12m/min；
（5）Rinsing displacement：Hollow-fibre membrane silk wound through driving wheel after enter potcher, with potcher built with hot water it is straight
Contact, in carrying out online rinsing processing at 45 DEG C, makes the solvent in film silk fully be exchanged with pure water, is replaced through rinsing
Afterwards, film silk is wound on wire drawing wheel；
（6）Heat treatment：Hollow-fibre membrane silk on wire drawing wheel is subjected to Length-fixing cutting, and uses pure water rinsed clean
Afterwards, film silk two ends are fixed, are put into heat treatment groove, in carrying out drawing and setting processing at 75 DEG C, stretch ratio is no more than 130%,
After drawn heat treatment 1.2 hours, film silk outward appearance is straight, is convenient for encapsulation process, while the membrane module that encapsulation is finished exists
Will not occur film silk shrinkage phenomenon during use again.
Step（1）In solvents mix for trimethyl phosphate 147g and propylene-glycol ethyl ether acetate 73g
Mixed solvent.
Step（1）In casting solution non-solvent mix for triethylene glycol 5g and glycerine 10g, step（2）In core liquid
Non-solvent is that triethylene glycol 50g and glycerine 70g is mixed, step（3）In outer solidification liquid non-solvent for triethylene glycol 50g and
Glycerine 70g is mixed.
Other be the same as Examples 1.
After tested, the fracture strength of gained polyvinylidene fluoride hollow fiber miillpore filter is 166MPa, and elongation at break is
300%, pure water flux 1971LMH@0.1MPa.
Embodiment 8：
A kind of preparation method of polyvinylidene fluoride hollow fiber miillpore filter, is comprised the following steps that：
（1）The preparation of casting solution：By PVDF resins 100g, solvents 240g, casting solution non-solvent 20g, polyvinyl pyrrole
Alkanone 12g, nanometer silicon carbide 5g are added in stirred tank in certain sequence, and in 160 DEG C of heating for dissolving of temperature, standing and defoaming 5 is small
When, form casting solution；
（2）The preparation of core liquid：Core liquid solvent 100g, core liquid non-solvent 140g, water 5g are added in core flow container, stirred at room temperature
Mix uniform, obtain interior solidification core liquid；
（3）Outer solidification liquid is prepared：Outer solidification liquid solvent 100g, outer solidification liquid non-solvent 140g, water 5g are added to coagulating tank
In, stir at room temperature, obtain outer solidification liquid；
（4）Spinning：By step（1）The casting solution of preparation is squeezed into spinning head, and spinneret temperature is 118 DEG C, from stirred tank to
Spinning head formation natural temperature gradient, while being passed through step（2）The core liquid of preparation, core liquid temperature control is between 25 DEG C, control
The range of flow of casting solution is 25ml/min, and the range of flow of core liquid is 9ml/min, after making casting solution by spinning head, is formed
The hollow form fiber of certain specification size, by 25mm dry journey distance with after air exchange, being coagulated into coagulating tank with outer
Solid-liquid is directly contacted, and coagulation bath temperature is controlled between 25 DEG C, while cooling, is carried out solvent-nonsolvent and is exchanged split-phase
Solidification, is formed with porous hollow-fibre membrane silk, the hollow fiber film thread come out from coagulating bath winds through driving wheel, left
Coagulating tank, spinning speed is controlled between 15m/min；
（5）Rinsing displacement：Hollow-fibre membrane silk wound through driving wheel after enter potcher, with potcher built with hot water it is straight
Contact, in carrying out online rinsing processing at 48 DEG C, makes the solvent in film silk fully be exchanged with pure water, is replaced through rinsing
Afterwards, film silk is wound on wire drawing wheel；
（6）Heat treatment：Hollow-fibre membrane silk on wire drawing wheel is subjected to Length-fixing cutting, and uses pure water rinsed clean
Afterwards, film silk two ends are fixed, are put into heat treatment groove, in carrying out drawing and setting processing at 78 DEG C, stretch ratio is no more than 130%,
After drawn heat treatment 1.4 hours, film silk outward appearance is straight, is convenient for encapsulation process, while the membrane module that encapsulation is finished exists
Will not occur film silk shrinkage phenomenon during use again.
Step（1）In solvents mix for trimethyl phosphate 150g and propylene-glycol ethyl ether acetate 90g
Mixed solvent.
Step（1）In casting solution non-solvent mix for propane diols 10g and ethylene glycol 10g, step（2）In core liquid
Non-solvent is that propane diols 70g and ethylene glycol 70g is mixed, step（3）In outer solidification liquid non-solvent be propane diols 70g and second
Glycol 70g is mixed.
Step（2）In core liquid solvent be triethyl phosphate 91g and ethylene glycol ether acetate 9g, step（3）In it is outer
Solidification liquid solvent is triethyl phosphate 91g and ethylene glycol ether acetate 9g.
Other be the same as Examples 1.
After tested, the fracture strength of gained polyvinylidene fluoride hollow fiber miillpore filter is 180MPa, and elongation at break is
310%, pure water flux 1867LMH@0.1MPa.
Embodiment 9：
A kind of preparation method of polyvinylidene fluoride hollow fiber miillpore filter, is comprised the following steps that：
（1）The preparation of casting solution：By PVDF resins 100g, solvents 260g, casting solution non-solvent 25g, polyvinyl pyrrole
Alkanone 15g, nanometer silicon carbide 6g are added in stirred tank in certain sequence, and in 170 DEG C of heating for dissolving of temperature, standing and defoaming 6 is small
When, form casting solution；
（2）The preparation of core liquid：Core liquid solvent 100g, core liquid non-solvent 160g, water 6g are added in core flow container, stirred at room temperature
Mix uniform, obtain interior solidification core liquid；
（3）Outer solidification liquid is prepared：Outer solidification liquid solvent 100g, outer solidification liquid non-solvent 160g, water 6g are added to coagulating tank
In, stir at room temperature, obtain outer solidification liquid；
（4）Spinning：By step（1）The casting solution of preparation is squeezed into spinning head, and spinneret temperature is 120 DEG C, from stirred tank to
Spinning head formation natural temperature gradient, while being passed through step（2）The core liquid of preparation, core liquid temperature control is between 28 DEG C, control
The range of flow of casting solution is 30ml/min, and the range of flow of core liquid is 11ml/min, after making casting solution by spinning head, is formed
The hollow form fiber of certain specification size, by 30mm dry journey distance with after air exchange, being coagulated into coagulating tank with outer
Solid-liquid is directly contacted, and coagulation bath temperature is controlled between 28 DEG C, while cooling, is carried out solvent-nonsolvent and is exchanged split-phase
Solidification, is formed with porous hollow-fibre membrane silk, the hollow fiber film thread come out from coagulating bath winds through driving wheel, left
Coagulating tank, spinning speed is controlled between 18m/min；
（5）Rinsing displacement：Hollow-fibre membrane silk wound through driving wheel after enter potcher, with potcher built with hot water it is straight
Contact, in carrying out online rinsing processing at 50 DEG C, makes the solvent in film silk fully be exchanged with pure water, is replaced through rinsing
Afterwards, film silk is wound on wire drawing wheel；
（6）Heat treatment：Hollow-fibre membrane silk on wire drawing wheel is subjected to Length-fixing cutting, and uses pure water rinsed clean
Afterwards, film silk two ends are fixed, are put into heat treatment groove, in carrying out drawing and setting processing at 80 DEG C, stretch ratio is no more than 130%,
After drawn heat treatment 1.6 hours, film silk outward appearance is straight, is convenient for encapsulation process, while the membrane module that encapsulation is finished exists
Will not occur film silk shrinkage phenomenon during use again.
Step（1）In solvents mix for trimethyl phosphate 144g and ethylene glycol ether acetate 116g
Mixed solvent.
Step（1）In casting solution non-solvent mix for glycerine 10g, diethylene glycol 5g and triethylene glycol 10g, step
（2）In core liquid non-solvent mix for glycerine 50g, diethylene glycol 60g and triethylene glycol 50g, step（3）In outer solidification
Liquid non-solvent is that glycerine 50g, diethylene glycol 60g and triethylene glycol 50g are mixed.
Step（2）In core liquid solvent mix for triethyl phosphate 77g and propylene-glycol ethyl ether acetate 23g, step
（3）In outer solidification liquid solvent mix for triethyl phosphate 77g and propylene-glycol ethyl ether acetate 23g.
Other be the same as Examples 1.
After tested, the fracture strength of gained polyvinylidene fluoride hollow fiber miillpore filter is 158MPa, and elongation at break is
290%, pure water flux 1946LMH@0.1MPa.
Embodiment 10：
A kind of preparation method of polyvinylidene fluoride hollow fiber miillpore filter, is comprised the following steps that：
（1）The preparation of casting solution：By PVDF resins 100g, solvents 280g, casting solution non-solvent 30g, polyvinyl pyrrole
Alkanone 18g, inorganic additive 8g are added in stirred tank in certain sequence, and in 180 DEG C of heating for dissolving of temperature, standing and defoaming 4 is small
When, form casting solution；
（2）The preparation of core liquid：Core liquid solvent 100g, core liquid non-solvent 180g, water 8g are added in core flow container, stirred at room temperature
Mix uniform, obtain interior solidification core liquid；
（3）Outer solidification liquid is prepared：Outer solidification liquid solvent 100g, outer solidification liquid non-solvent 180g, water 8g are added to coagulating tank
In, stir at room temperature, obtain outer solidification liquid；
（4）Spinning：By step（1）The casting solution of preparation is squeezed into spinning head, and spinneret temperature is 125 DEG C, from stirred tank to
Spinning head formation natural temperature gradient, while being passed through step（2）The core liquid of preparation, core liquid temperature control is between 30 DEG C, control
The range of flow of casting solution is 35ml/min, and the range of flow of core liquid is 13ml/min, after making casting solution by spinning head, is formed
The hollow form fiber of certain specification size, by 40mm dry journey distance with after air exchange, being coagulated into coagulating tank with outer
Solid-liquid is directly contacted, and coagulation bath temperature is controlled between 30 DEG C, while cooling, is carried out solvent-nonsolvent and is exchanged split-phase
Solidification, is formed with porous hollow-fibre membrane silk, the hollow fiber film thread come out from coagulating bath winds through driving wheel, left
Coagulating tank, spinning speed is controlled between 20m/min；
（5）Rinsing displacement：Hollow-fibre membrane silk wound through driving wheel after enter potcher, with potcher built with hot water it is straight
Contact, in carrying out online rinsing processing at 55 DEG C, makes the solvent in film silk fully be exchanged with pure water, is replaced through rinsing
Afterwards, film silk is wound on wire drawing wheel；
（6）Heat treatment：Hollow-fibre membrane silk on wire drawing wheel is subjected to Length-fixing cutting, and uses pure water rinsed clean
Afterwards, film silk two ends are fixed, are put into heat treatment groove, in carrying out drawing and setting processing at 85 DEG C, stretch ratio is no more than 130%,
After drawn heat treatment 1.8 hours, film silk outward appearance is straight, is convenient for encapsulation process, while the membrane module that encapsulation is finished exists
Will not occur film silk shrinkage phenomenon during use again.
Step（1）In solvents mix for triethyl phosphate 147g and ethylene glycol ether acetate 133g
Mixed solvent.
Step（1）In casting solution non-solvent for glycerine 10g, diethylene glycol 5g, propane diols 5g and triethylene glycol 10g mixing
Form, step（2）In core liquid non-solvent for glycerine 50g, diethylene glycol 60g, propane diols 20g and triethylene glycol 50g mixing and
Into step（3）In outer solidification liquid non-solvent for glycerine 50g, diethylene glycol 60g, propane diols 20g and triethylene glycol 50g mixing
Form.
Step（1）In inorganic additive be nanometer silicon carbide 4g and nano-glass 4g.
Step（2）In core liquid solvent mix for trimethyl phosphate 62g and propylene-glycol ethyl ether acetate 38g, step
（3）In outer solidification liquid solvent mix for trimethyl phosphate 62g and propylene-glycol ethyl ether acetate 38g.
Other be the same as Examples 1.
After tested, the fracture strength of gained polyvinylidene fluoride hollow fiber miillpore filter is 174MPa, and elongation at break is
340%, pure water flux 2051LMH@0.1MPa.
Embodiment 11：
A kind of preparation method of polyvinylidene fluoride hollow fiber miillpore filter, is comprised the following steps that：
（1）The preparation of casting solution：By PVDF resins 100g, solvents 300g, casting solution non-solvent 40g, polyvinyl pyrrole
Alkanone 20g, inorganic additive 10g are added in stirred tank in certain sequence, and in 186 DEG C of heating for dissolving of temperature, standing and defoaming 5 is small
When, form casting solution；
（2）The preparation of core liquid：Core liquid solvent 100g, core liquid non-solvent 200g, water 10g are added in core flow container, at room temperature
Stir, obtain interior solidification core liquid；
（3）Outer solidification liquid is prepared：Outer solidification liquid solvent 100g, outer solidification liquid non-solvent 200g, water 10g are added to coagulating tank
In, stir at room temperature, obtain outer solidification liquid；
（4）Spinning：By step（1）The casting solution of preparation is squeezed into spinning head, and spinneret temperature is 130 DEG C, from stirred tank to
Spinning head formation natural temperature gradient, while being passed through step（2）The core liquid of preparation, core liquid temperature control is between 35 DEG C, control
The range of flow of casting solution is 40ml/min, and the range of flow of core liquid is 15ml/min, after making casting solution by spinning head, is formed
The hollow form fiber of certain specification size, by 50mm dry journey distance with after air exchange, being coagulated into coagulating tank with outer
Solid-liquid is directly contacted, and coagulation bath temperature is controlled between 35 DEG C, while cooling, is carried out solvent-nonsolvent and is exchanged split-phase
Solidification, is formed with porous hollow-fibre membrane silk, the hollow fiber film thread come out from coagulating bath winds through driving wheel, left
Coagulating tank, spinning speed is controlled between 25m/min；
（5）Rinsing displacement：Hollow-fibre membrane silk wound through driving wheel after enter potcher, with potcher built with hot water it is straight
Contact, in carrying out online rinsing processing at 60 DEG C, makes the solvent in film silk fully be exchanged with pure water, is replaced through rinsing
Afterwards, film silk is wound on wire drawing wheel；
（6）Heat treatment：Hollow-fibre membrane silk on wire drawing wheel is subjected to Length-fixing cutting, and uses pure water rinsed clean
Afterwards, film silk two ends are fixed, are put into heat treatment groove, in carrying out drawing and setting processing at 90 DEG C, stretch ratio is no more than 130%,
After drawn heat treatment 2 hours, film silk outward appearance is straight, is convenient for encapsulation process, while the membrane module that encapsulation is finished makes
Will not occur film silk shrinkage phenomenon again during.
Step（1）In solvents mix for triethyl phosphate 150g and propylene-glycol ethyl ether acetate 150g
Mixed solvent.
Step（1）In casting solution non-solvent be glycerine 10g, ethylene glycol 10g, diethylene glycol 5g, propane diols 5g and three second
Glycol 10g is mixed, step（2）In core liquid non-solvent be glycerine 50g, ethylene glycol 20g, diethylene glycol 60g, propane diols
20g and triethylene glycol 50g are mixed, step（3）In outer solidification liquid non-solvent be glycerine 50g, ethylene glycol 20g, diethyl two
Alcohol 60g, propane diols 20g and triethylene glycol 50g are mixed.
Step（1）In inorganic additive be nanometer silicon carbide 5g and nano-glass 5g.
Step（2）In core liquid solvent mix for trimethyl phosphate 50g and ethylene glycol ether acetate 50g, step
（3）In outer solidification liquid solvent mix for trimethyl phosphate 50g and ethylene glycol ether acetate 50g.
Other be the same as Examples 1.
After tested, the fracture strength of gained polyvinylidene fluoride hollow fiber miillpore filter is 162MPa, and elongation at break is
320%, pure water flux 1845LMH@0.1MPa.
Embodiment 12：
A kind of preparation method of PVDF doughnut miillpore filters for sewage disposal：
1）It is prepared by casting solution：PVDF powder 60g, triethyl phosphate 120g, polyvinyl acetate 6g, glycerine 12g, in certain sequence
It is added in stirred tank, stirs, be gradually heating to 145 DEG C, stir 4 hours, stop stirring, standing and defoaming 4 hours stands process
Middle holding temperature in the kettle.
2）Core liquid：In triethyl phosphate and diethylene glycol ratio 1:1 prepares spinning core liquid, stirs, is transferred to a high position
In core liquid bath.
3）Solidification liquid：It is identical with core liquid configuration proportion.
4）Spinning condition：116 DEG C of spinneret temperature, 30 DEG C of core liquid temperature degree, 5 DEG C of solidification liquid temperature, stirred tank is passed through argon gas,
Pressure 0.1MPa, 12 revs/min of active wheel speed, spinning head to 5 centimetres of solidification liquid liquid level distance, 1.5 meters of coagulating bath depth.Feed liquid
Into after coagulating bath, film silk is depressed into coagulating bath bottom with wire pressing device, and wind to come out from coagulating bath by driving wheel
Film silk be fully cured, be translucent shape.
5）Rinsing displacement：Translucent film silk enters potcher, and temperature 45 C accelerates wherein solvent to be handed over pure water
Change, after potcher comes out, film silk is wound up on wire drawing wheel by film silk transparency reduction.
6）Heat treatment：Spinning terminates, and film silk scale is blocked, draining is collected, is put into 35 DEG C of pure water and rinses twice, tie up
After load drawing die, in 80 DEG C of heat treatment grooves drawing and setting handle 30 minutes, The final draw ratio example be 120%.
Film silk external diameter 1.3mm, internal diameter 0.9mm are finally given, after tested, its fracture strength is 108MPa, elongation at break
For 350%, pure water flux 864LMH@0.1MPa.Flux drops to 46.1% after film silk compresses through 0.25MPa pressure（398 LMH）,
Film silk compression is after recoil, flux recovery to 53.7%（464 LMH）.
Film silk derived above is packaged into the MBR membrane modules that effective area is 2.5 square meters, installed in film-biological respinse
In device pilot plant, the experiment condition is controlled to be：Raw water is sanitary sewage, pH7-8, and reinforcing ventilation gas-water ratio is（25-100）:1,
Suspended sediment concentration MLSS5000-10000mg/L in reactor, timing aspirate, swabbing pressure control 0.01-0.03MPa it
Between, pressure carries out automatic back-washing more than 0.03MPa, when reaction tank sludge concentration is more than 10000mg/L progress spoil disposals, by regular
Detection production water turbidity and COD judge film silk integrality.The pilot plant test is carried out continuously 60 days, and when operation was to 37 days, production water is turbid
Degree and COD are raised suddenly, on inspection, it is found that membrane module film silk does not substantially shrink, but find there are indivedual fracture of wire phenomenons.
Embodiment 13：
A kind of preparation method of PVDF doughnut miillpore filters for sewage disposal：
1）It is prepared by casting solution：The g of PVDF powder 60, the g of triethyl phosphate 80, the g of propylene-glycol ethyl ether acetate 30, polyvinyl pyrrole
The g of alkanone 5, the g of glycerine 10, the g of Nano glass powder 5, are added in stirred tank in certain sequence, stirring, are gradually heating to 155 DEG C,
Stirring 6 hours, stops stirring, and standing and defoaming 4 hours keeps temperature in the kettle during standing.
2）Core liquid：In triethyl phosphate and diethylene glycol ratio 1:1 prepares spinning core liquid, stirs, is transferred to a high position
In core liquid bath.
3）Solidification liquid：It is identical with core liquid configuration proportion.
4）Spinning condition：122 DEG C of spinneret temperature, 30 DEG C of core liquid temperature degree, 10 DEG C of solidification liquid temperature, 10 meters of spinning speed/
Point, do 5 centimetres of journey, 1.5 meters of coagulating bath depth.Feed liquid enters after coagulating bath, and film silk is depressed into coagulating bath bottom with wire pressing device,
And wound by driving wheel come the film silk come out from coagulating bath is fully cured, and be translucent shape.
5）Rinsing displacement：Translucent film silk enters potcher, and temperature 45 C accelerates wherein solvent to be handed over pure water
Change, after potcher comes out, film silk transparency reduction, is white.
6）Heat treatment：Spinning terminates, and film silk scale is blocked, draining is collected, is put into 35 DEG C of pure water and rinses twice, tie up
After load drawing die, in 80 DEG C of heat treatment grooves drawing and setting handle 60 minutes, The final draw ratio example be 130%.
Film silk external diameter 1.25mm, internal diameter 0.88mm are finally given, after tested, its fracture strength is 158MPa, extension at break
Rate is 320%, pure water flux 1642LMH@0.1MPa.Pure water flux drops to 73.8% after film silk compresses through 0.25MPa pressure
（1213LMH）, film silk compression is after recoil, and pure water flux returns to 83.7%（1375LMH）.
Pilot plant test is continuously run 60 days, does not find that production water turbidity and COD are abnormal, and the inspection membrane module film silk that expires is not bright
It is aobvious to shrink, there is no fracture of wire phenomenon.
Embodiment 14：
A kind of preparation method of PVDF doughnut miillpore filters for sewage disposal：
1）It is prepared by casting solution：The g of PVDF powder 60, the g of trimethyl phosphate 100, the g of ethylene glycol ether acetate 60, polyvinyl pyrrole
The g of alkanone 5, the g of glycerine 5, the g of Nano glass powder 10, are added in stirred tank in certain sequence, stirring, are gradually heating to 168 DEG C,
Stirring 4 hours, stops stirring, and standing and defoaming 4 hours keeps temperature in the kettle during standing.
2）Core liquid：In triethyl phosphate and diethylene glycol ratio 1:1 prepares spinning core liquid, stirs, is transferred to a high position
In core liquid bath.
3）Solidification liquid：It is identical with core liquid configuration proportion.
4）Spinning condition：125 DEG C of spinneret temperature, 30 DEG C of core liquid temperature degree, 25 DEG C of solidification liquid temperature, 15 meters of spinning speed/
Point, do 5 centimetres of journey, 1.5 meters of coagulating bath depth.Feed liquid enters after coagulating bath, and film silk is depressed into coagulating bath bottom with wire pressing device,
And wound by driving wheel come the film silk come out from coagulating bath is fully cured, and be translucent shape.
5）Rinsing displacement：Translucent film silk enters potcher, and temperature 45 C accelerates wherein solvent to be handed over pure water
Change, after potcher comes out, film silk transparency reduction, is white.
6）Heat treatment：Spinning terminates, and film silk scale is blocked, draining is collected, is put into 35 DEG C of pure water and rinses twice, tie up
After load drawing die, in 80 DEG C of heat treatment grooves drawing and setting handle 60 minutes, The final draw ratio example be 130%.
Film silk external diameter 1.25mm, internal diameter 0.88mm are finally given, after tested, its fracture strength is 166MPa, extension at break
Rate is 300%, pure water flux 1971LMH@0.1MPa.Pure water flux drops to 69.1% after film silk compresses through 0.25MPa pressure
（1362LMH）, film silk compression is after recoil, and pure water flux returns to 81.2%（1600LMH）.
Pilot plant test is continuously run 60 days, does not find that production water turbidity and COD are abnormal, and the inspection membrane module film silk that expires is not bright
It is aobvious to shrink, there is no fracture of wire phenomenon.
Above-described is only the preferred embodiment of the present invention, it is noted that for those skilled in the art,
Under the premise of general idea of the present invention is not departed from, some changes and improvements can also be made, these should also be considered as the present invention's
Protection domain.
Claims (10)
1. a kind of preparation method of polyvinylidene fluoride hollow fiber miillpore filter, it is characterised in that：Comprise the following steps that：
（1）The preparation of casting solution：By PVDF resins, solvents, casting solution non-solvent, hydrophilic modifier, inorganic additive
In mass ratio 1:（1.6-3.0）:（0.02-0.4）:（0.01-0.2）:（0-0.1）Ratio be added in stirred tank, in temperature
128-186 DEG C of heating for dissolving, standing and defoaming 4-6 hours forms casting solution；
（2）The preparation of core liquid：By core liquid solvent, core liquid non-solvent and water in mass ratio 1:（0.5-2.0）:（0-0.1）Ratio
It is added in core flow container, stirs at room temperature, obtains interior solidification core liquid；
（3）Outer solidification liquid is prepared：By outer solidification liquid solvent, outer solidification liquid non-solvent and water in mass ratio 1:（0.5-2.0）:（0-
0.1）Ratio be added in coagulating tank, stir at room temperature, obtain outer solidification liquid；
（4）Spinning：By step（1）The casting solution of preparation is squeezed into spinning head, while being passed through step（2）The core liquid of preparation, control
The range of flow of casting solution processed is 8-40ml/min, and the range of flow of core liquid is 3-15ml/min, casting solution is passed through spinning head
Afterwards, form the hollow form fiber of certain specification size, by 5-50mm dry journey distance with after air exchange, into coagulating tank
In directly contacted with outer solidification liquid, while cooling, carry out solvent-nonsolvent exchange split-phase solidification, formed have it is porous
Hollow-fibre membrane silk, the hollow fiber film thread come out from coagulating bath winds through driving wheel, leaves coagulating tank；
（5）Rinsing displacement：Hollow-fibre membrane silk wound through driving wheel after enter potcher, with potcher built with hot water
Directly contact, in carrying out online rinsing processing at 30-60 DEG C, the solvent in film silk is fully exchanged with pure water, through rinsing
After displacement, film silk is wound on wire drawing wheel；
（6）Heat treatment：Hollow-fibre membrane silk on wire drawing wheel is subjected to Length-fixing cutting, and uses pure water rinsed clean
Afterwards, film silk two ends are fixed, be put into heat treatment groove, in carrying out drawing and setting processing at 60-90 DEG C, stretch ratio is no more than
130%, drawn heat treatment 0.5-2 hours.
2. the preparation method of polyvinylidene fluoride hollow fiber miillpore filter according to claim 1, it is characterised in that：It is described
Step（1）In solvents be triethyl phosphate or trimethyl phosphate and ethylene glycol ether acetate or propylene-glycol ethyl ether vinegar
Acid esters is 1 in mass ratio:（0.1-1）The mixed solvent mixed.
3. the preparation method of polyvinylidene fluoride hollow fiber miillpore filter according to claim 1, it is characterised in that：It is described
Step（1）In casting solution non-solvent, step（2）In core liquid non-solvent and step（3）In outer solidification liquid non-solvent be
At least one of glycerine, propane diols, ethylene glycol, diethylene glycol or triethylene glycol.
4. the preparation method of polyvinylidene fluoride hollow fiber miillpore filter according to claim 1, it is characterised in that：It is described
Step（1）In hydrophilic modifier be polyvinyl acetate or polyvinylpyrrolidone.
5. the preparation method of polyvinylidene fluoride hollow fiber miillpore filter according to claim 1, it is characterised in that：It is described
Step（1）In inorganic additive at least one of for nano-glass, nanometer silicon carbide.
6. the preparation method of polyvinylidene fluoride hollow fiber miillpore filter according to claim 1, it is characterised in that：It is described
Step（2）In core liquid solvent and step（3）In outer solidification liquid solvent be triethyl phosphate or trimethyl phosphate, Huo Zhewei
Triethyl phosphate or trimethyl phosphate and ethylene glycol ether acetate or propylene-glycol ethyl ether acetate are 1 in mass ratio:（0.1-1）
The mixed solvent mixed.
7. the preparation method of polyvinylidene fluoride hollow fiber miillpore filter according to claim 1, it is characterised in that：Work as institute
Spinning be outer press mold when, the step（3）In outer solidification liquid in add outer solidification liquid gross mass 0.1-1% water.
8. the preparation method of polyvinylidene fluoride hollow fiber miillpore filter according to claim 1, it is characterised in that：It is described
Step（4）In spinneret temperature be 100-130 DEG C, from stirred tank to spinning head formed natural temperature gradient, core liquid temperature degree control
System is between 10-35 DEG C, and coagulation bath temperature is controlled between 5-35 DEG C, and spinning speed is controlled between 5-25m/min.
9. the preparation method of polyvinylidene fluoride hollow fiber miillpore filter according to claim 1, it is characterised in that：Work as institute
Spinning be interior press mold when, the step（2）In core liquid in add core liquid gross mass 0.1-1% water.
10. prepared by the preparation method of the polyvinylidene fluoride hollow fiber miillpore filter according to claim any one of 1-9
Polyvinylidene fluoride hollow fiber miillpore filter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710354891.4A CN107096396B (en) | 2017-05-19 | 2017-05-19 | Polyvinylidene fluoride hollow fiber microporous filter membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710354891.4A CN107096396B (en) | 2017-05-19 | 2017-05-19 | Polyvinylidene fluoride hollow fiber microporous filter membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107096396A true CN107096396A (en) | 2017-08-29 |
| CN107096396B CN107096396B (en) | 2021-03-19 |
Family
ID=59669435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710354891.4A Active CN107096396B (en) | 2017-05-19 | 2017-05-19 | Polyvinylidene fluoride hollow fiber microporous filter membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107096396B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108031305A (en) * | 2017-12-23 | 2018-05-15 | 刘顶康 | A kind of method for extending polyolefin microfiltration membranes Durability of antimicrobial effect |
| CN108786468A (en) * | 2018-06-26 | 2018-11-13 | 黑龙江大学 | A kind of method that the thermotropic phase inversion of low temperature prepares flushing-free PVDF tube-type micropore films |
| CN109916782A (en) * | 2019-03-13 | 2019-06-21 | 湖南省天骑医学新技术股份有限公司 | A method of it is detected using miillpore filter |
| CN112058095A (en) * | 2020-09-23 | 2020-12-11 | 天津城建大学 | Preparation method of internal pressure type non-isometric hollow fiber membrane and fiber membrane component |
| CN112672813A (en) * | 2019-02-28 | 2021-04-16 | 东洋纺株式会社 | Hollow fiber membrane and method for producing hollow fiber membrane |
| CN112892217A (en) * | 2021-01-18 | 2021-06-04 | 华电水务装备(天津)有限公司 | Hollow fiber homogeneous ultrafiltration membrane wire and preparation method thereof |
| CN113200855A (en) * | 2021-05-13 | 2021-08-03 | 江苏巨莱生物医药有限公司 | Preparation method of ethyl benzoylacetate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101370572A (en) * | 2006-01-11 | 2009-02-18 | 东洋纺织株式会社 | Polyvinylidene fluoride hollow yarn type microporous film and process for production of the same |
| CN101396641A (en) * | 2008-10-31 | 2009-04-01 | 孟广祯 | Composite thermotropic phase separation film-making method |
| CN102357346A (en) * | 2011-11-07 | 2012-02-22 | 东华大学 | Polyvinylidene fluoride hollow fiber membrane, preparation method and application |
-
2017
- 2017-05-19 CN CN201710354891.4A patent/CN107096396B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101370572A (en) * | 2006-01-11 | 2009-02-18 | 东洋纺织株式会社 | Polyvinylidene fluoride hollow yarn type microporous film and process for production of the same |
| CN101396641A (en) * | 2008-10-31 | 2009-04-01 | 孟广祯 | Composite thermotropic phase separation film-making method |
| CN102357346A (en) * | 2011-11-07 | 2012-02-22 | 东华大学 | Polyvinylidene fluoride hollow fiber membrane, preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 董秉直等: "《饮用水膜法处理新技术》", 30 September 2015, 同济大学出版社 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108031305A (en) * | 2017-12-23 | 2018-05-15 | 刘顶康 | A kind of method for extending polyolefin microfiltration membranes Durability of antimicrobial effect |
| CN108786468A (en) * | 2018-06-26 | 2018-11-13 | 黑龙江大学 | A kind of method that the thermotropic phase inversion of low temperature prepares flushing-free PVDF tube-type micropore films |
| CN112672813A (en) * | 2019-02-28 | 2021-04-16 | 东洋纺株式会社 | Hollow fiber membrane and method for producing hollow fiber membrane |
| CN109916782A (en) * | 2019-03-13 | 2019-06-21 | 湖南省天骑医学新技术股份有限公司 | A method of it is detected using miillpore filter |
| CN112058095A (en) * | 2020-09-23 | 2020-12-11 | 天津城建大学 | Preparation method of internal pressure type non-isometric hollow fiber membrane and fiber membrane component |
| CN112892217A (en) * | 2021-01-18 | 2021-06-04 | 华电水务装备(天津)有限公司 | Hollow fiber homogeneous ultrafiltration membrane wire and preparation method thereof |
| CN113200855A (en) * | 2021-05-13 | 2021-08-03 | 江苏巨莱生物医药有限公司 | Preparation method of ethyl benzoylacetate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107096396B (en) | 2021-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107096396A (en) | A kind of polyvinylidene fluoride hollow fiber miillpore filter and preparation method thereof | |
| CN101945695B (en) | Polyamide hollow fiber membrane and method for producing same | |
| CN107096395A (en) | A kind of reinforced type polyvinylidene fluoride hollow fiber miillpore filter and preparation method thereof | |
| WO2016115908A1 (en) | Polyvinylidene fluoride hollow fibre membrane of in-situ pore-forming agent and preparation method therefor | |
| CN102068918B (en) | Hydrophilic polyethylene hollow fiber membrane and preparation method thereof | |
| CN101623601A (en) | Method for preparing compound hollow fibrous membrane | |
| CN102107121A (en) | Method for preparing hollow fiber microporous membrane by thermally-induced phase separation method | |
| CN101485961A (en) | Method for preparing polyvinylidene fluoride hollow fiber alloy film | |
| CN108159898A (en) | The method that thermally induced phase separation prepares polyacrylonitrile-radical microporous barrier | |
| CN101961611B (en) | Hollow polyester fiber microporous membrane and preparation method thereof | |
| CN103894079A (en) | Method for preparing polyurethane-based hollow fiber ultrafiltration membrane and product thereof | |
| CN101890304B (en) | Porous membrane with three-dimensional interpenetrating polymer network and preparation method | |
| CN101890303B (en) | Hollow fibrous membrane with asymmetrical structure and preparation method thereof | |
| CN101890309B (en) | Method for preparing hollow fiber membranes by using thermally induced phase separation (TIPS) process | |
| CN111514765A (en) | Preparation method of MIL-101(Fe) -doped straw-based cellulose acetate composite membrane | |
| CN106883447B (en) | A kind of application of high-strength polymer film, preparation method and diluent | |
| CN102357346B (en) | Polyvinylidene fluoride hollow fiber membrane, preparation method and application | |
| CN103638830B (en) | For the preparation method of the hot method Pvdf Microporous Hollow Fiber Membrane of drinking water treatment | |
| CN101879417B (en) | Hollow fiber membrane containing PMMA (Polymethyl Methacrylate) and preparation method thereof | |
| CN103638833B (en) | A kind of preparation method of the large flux hollow fiber membranes for drink water purifying | |
| CN103055720A (en) | Hydrophilic modified PVDF and PU mixed taper hole ultrafilteration membrane and preparation method thereof | |
| CN101322921A (en) | Process for manufacturing PVC hollow fiber fillm | |
| CN103638831B (en) | For the preparation method of the polyvinylidene fluoride hollow fiber ultrafiltration membrane of drinking water treatment | |
| CN101920173B (en) | Ultrafiltration membrane using ethylene glycol carbonic ester and diethylene glycol as diluent and manufacturing method thereof | |
| CN103638828B (en) | Be used for the preparation method of the ultralow pressure polyvinylidene fluoride alloy membrane of drinking water treatment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |