CN105642132A - Targeted synergized and nanometer functional material modified polyvinylidene fluoride membrane and preparation method thereof - Google Patents
Targeted synergized and nanometer functional material modified polyvinylidene fluoride membrane and preparation method thereof Download PDFInfo
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- CN105642132A CN105642132A CN201610235576.5A CN201610235576A CN105642132A CN 105642132 A CN105642132 A CN 105642132A CN 201610235576 A CN201610235576 A CN 201610235576A CN 105642132 A CN105642132 A CN 105642132A
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- 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
- 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
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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
- B01D69/06—Flat membranes
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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
- B01D69/087—Details relating to the spinning process
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/39—Electrospinning
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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
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Abstract
The invention relates to a targeted synergized and nanometer functional material modified polyvinylidene fluoride membrane and a preparation method thereof. The nanometer functional material is a nanometer TiO2 dispersion solution system prepared by a supercritical fluid method; a mixture of nanometer functional master batch and graphene in a weight ratio of (3:1)-(1:3) is preferably used in the polyvinylidene fluoride membrane; the specific nanometer functional master batch is used for well controlling the nanoparticle size, thereby improving the dispersibility of the nanometer material, further improving the hydrophilicity and permeability of the membrane, increasing the pure water flux of the membrane by 15% or more, inhibiting the formation of macropores of the membrane to a certain extent, and increasing the porosity; the addition of the hydrophilic nanometer functional master batch can improve the hydrophilicity of the membrane, reduce the contamination in an MBR (Membrane Biological Reactor) operating process, reduce the cleaning number and strength and prolong the service life of the membrane; and the addition of the nanometer functional master batch has no influence on the microstructure of the membrane and does not destroy the original properties of the polyvinylidene fluoride membrane.
Description
[technical field]
The present invention relates to polyvinylidene fluoride film, particularly relate to a kind of polyvinylidene fluoride film modified through targeting potentiation nano-functional material, with and preparation method thereof.
[background technology]
At present in conventional membrane material, Kynoar (PVDF), there is good heat stability, chemical stability, radiation resistance and excellent mechanical performance and low price, thus paid close attention to widely. But owing to its surface can be low, the film hydrophilic prepared is poor, easily by the contaminating impurity in water in water treatment procedure, such as larger molecular organics, microorganism etc. Make membrane flux reduce and can not recover, cause processing in running at water, backwash and the problem such as the stop cleaning time is more, significantly limit it in the popularization of water factory and use. So it is very necessary to improve performance that pvdf membrane carries out hydrophilic modifying.
Generally can be improved the antifouling property of film by physically or chemically means, current method of modifying can be divided mainly into membrane surface modification and membrane material modified two big classes. Not only blended ultrafiltration is modified due to easy and simple to handle, excellent performance, effective, and easily realization but also economical and practical, is always up obtaining the common method of new modified membrane material. Organic and inorganic blending operations is simple, excellent performance, and adding hydrophilic inorganic nano-particle can increase the hydrophilic of film, reduces the pollution of ultrafilter membrane, increases the mechanical performance of film simultaneously, be the focus of Recent study. It is currently used for the inorganic nano material of Kynoar membrane modifying mainly to have in Al2O3, SiO2, TiO2, ZrO2 nano-particle, particularly CN201310014691.6 to it is mentioned that the mixture adopting oxide/carbon nanometer tube and graphene oxide is to prepare polyvinylidene fluoride modified separation film; But the inorganic nanoparticles of these routines is when configuring casting solution, nano-particle all exist be susceptible to reunite, the problem of bad dispersibility in casting solution, reduce the dimensional effect of nano-particle, cause the ultrafilter membrane hydrophilic prepared to improve effect bad, and the nano-particle reunited easily blocks fenestra and reduces water flux.
The applicant is surprisingly found that, carrys out modified polyvinilidene fluoride and can prepare hydrophilic, superior permeability when adopting a kind of PVDF (i.e. Kynoar) targeting potentiation nano functional masterbatch that is exclusively used in processed through special process and can control the polyvinylidene fluoride film of nanoparticles size size.
[summary of the invention]
When it is an object of the invention to overcome existing interpolation inorganic nanoparticles modified polyvinilidene fluoride, existing nano-particle is susceptible to reunite, finally can not control the size of nanoparticles size, and then make obtained polyvinylidene fluoride film hydrophilically, superior permeability; The method technique preparing this polyvinylidene fluoride film is simple, be prone to amplify and produce.
For achieving the above object, the present invention provides a kind of polyvinylidene fluoride film modified through targeting potentiation nano-functional material, it is characterised in that described modified polyvinylidene fluoride film is made up of the following raw materials according with parts by weight:
Described solvent is N, at least one or multiple in N dimethyl acetamide, dimethylformamide and N-Methyl pyrrolidone;
Described porogen is polyvinylpyrrolidone, Polyethylene Glycol, ethylene glycol or anhydrous Lithium chloride
Described nano functional masterbatch is the nano-TiO adopting following supercritical fluid processes to prepare2Dispersion liquid system:
By nano-TiO2Powder body, dehydrated alcohol, acetylacetone,2,4-pentanedione, triton x-100, and the mixed liquor of CuPc or FePC and N, N-dimethyl acetylamide joins in supercritical reaction still by the mass ratio of 1:100��1:0.03��0.1:0.03��0.1:0.003��0.01, wherein CuPc or FePC and N, N-dimethyl acetylamide are by weight stirring mixed processing at normal temperatures and pressures in advance for 1:2, reactor is heated to 30-100 DEG C, stirring and dissolving 15-60min, rotating speed 150-350rpm; CO by refrigeration to 5-8 DEG C2Being passed in reactor after the intensified pump supercharging of fluid, be under 100-350rpm in 31-100 DEG C of temperature and 7.14-10.0MPa pressure, speed of agitator, the supercritical time is not less than 5min; Then in coil pipe U-shaped in reactor, pass into 20-25 DEG C of recirculated cooling water and carry out decrease temperature and pressure, water velocity is 100-120ml/min, when in still, pressure and temperature is down to 5.2-4.8MPa and 36-32 DEG C respectively, it is exhausted decompression, exhaust velocity is 30-120ml/min, to still during pressure 1.0-0MPa, open bleeder valve, obtain nano-TiO2Dispersion liquid system.
Preferably, described solvent is N, N dimethyl acetamide;
Preferably, described porogen is polyvinylpyrrolidone and Polyethylene Glycol;
Preferably, described modified polyvinylidene fluoride film is made up of the following raw materials according with parts by weight:
Further, the preparation method that the present invention provides above-mentioned polyvinylidene fluoride film, it is characterised in that said method comprising the steps of:
(1) by pre-dispersed for nano functional masterbatch in a solvent, and utilize ultrasonic cell disintegration instrument to carry out ultrasonic disperse 1-3h;
(2) Kynoar and porogen are dissolved in a solvent, until completely dissolved, add the nano functional masterbatch being dispersed through of step (1), stir dispersed in the solution to it;
(3), after obtained solution being stirred 8-16h at 60-80 DEG C, take out negative pressure deaeration 1-6h, obtain the casting solution after deaeration;
(4) by described casting solution 15-30 DEG C, utilize under 30%-60% humidity dry-wet method to carry out spinning, spinning temperature is 50-80 DEG C, coagulating bath film-forming is entered by spinneret after being extruded by casting solution, coagulation bath temperature is 40-80 DEG C, air bath is highly 10-40cm, spinning speed is 10-30m/min, prepares the film of spinning; Described coagulation bath composition is the water of the solvent of 10-30,70-90 in parts by weight, and described solvent is N, N dimethyl acetamide, dimethylformamide and N-Methyl pyrrolidone, it is preferable that N, N dimethyl acetamide;
(5), after the film of spinning being soaked 12-24h in pure water, polyvinylidene fluoride film is prepared.
Further, inventor have found that, being used for the polyvinylidene fluoride film that the application can make to prepare with Graphene after being coordinated with specific ratio by the nano functional masterbatch of the application more excellent in hydrophilic, permeability, the weight ratio of the two is 3:1-1:3, it is preferred to 1:1.
The polyvinylidene fluoride film of the present invention can be Flat Membrane, doughnut homogeneous membrane, doughnut liner reinforcing membrane according to form; Can be micro-filtration membrane, ultrafilter membrane or NF membrane according to hole size.
Specific nano functional masterbatch is adopted: all the other are different from nano-particle conventional at present, and described nano functional masterbatch joins in the casting solution in PVDF membrane for water treatment preparation process by a certain percentage, makes function TiO about the present invention2Nano material dispersion is more uniform, and the pvdf membrane surface of preparation is more smooth, has biocidal property, is conducive to the raising of membrane for water treatment water flux and resistance tocrocking.
Coordinate with special ratios with Graphene about adopting nano functional masterbatch, on the one hand, Graphene itself and nano functional masterbatch have the good compatibility, form stable structure, therefore can effectively suppress the reunion between identical nanostructure; On the other hand, Graphene is applied to this kind of polyvinylidene fluoride film with nano functional masterbatch after coordinating with specific ratio, compares that be used alone can the hydrophilic of reinforcing membrane and contamination resistance further so that the effluent flux of film is improved further.
In sum:
The invention have the advantage that
(1) adopt specific nano functional masterbatch, it is possible to better control over nanoparticles size size, improve nano material dispersibility;
(2) common nano-particle is compared so that hydrophilic and the permeability of film all improve further; The pure water flux that can make film improves more than 15%;
(3) operation safety and stability, no solvent residue, three-waste free discharge, and be prone to amplify production;
(4) use nano functional masterbatch, the macropore of film can be suppressed to a certain extent to be formed, improve porosity;
(5) add this hydrophilic nano functional master batch, it is possible to increase film silk hydrophilic, reduce its pollution in MBR running, reduce wash number and intensity, extend film silk service life; The microstructure on film that adds of this nano functional masterbatch simultaneously does not produce impact, does not destroy the original performance of polyvinylidene fluoride film.
[accompanying drawing explanation]
Fig. 1: add the high power surfaces externally and internally electron scanning micrograph of pvdf membrane after nano functional masterbatch of the present invention;
Fig. 2: add the densification reinforced effects test result of nano functional masterbatch caudacoria of the present invention;
Fig. 3,4 be in MBR reinforcing membrane add nano functional masterbatch caudacoria silk run antifouling property.
[detailed description of the invention]
Below in conjunction with drawings and Examples, the detailed description of the invention of invention is described in further detail. Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.
Embodiment 1:
Following supercritical fluid processes is adopted to prepare nano-TiO2Dispersion liquid system:
Weigh nano-TiO2Powder body (P25) 30g, dehydrated alcohol 390g, acetylacetone,2,4-pentanedione 2.1g, triton x-100 1.5g, (CuPc/DMAC mass ratio is 1:2 to CuPc/DMAC mixed liquor 0.45g, stirring mixing at normal temperatures and pressures 1 hour in advance), it is sequentially placed in reactor; Reactor is heated to 45 DEG C, speed of agitator 300rpm, dissolves 30min;Then by the CO of refrigeration to 5-6 DEG C2Being passed in reactor after the intensified pump supercharging of fluid, temperature during supercritical is maintained at 45 DEG C, and reactor pressure is 8.5MPa, is under 150rpm at speed of agitator, supercritical 30min; U-shaped coil pipe passes into 20-25 DEG C of recirculated cooling water in reactor, water velocity is 100-120ml/min, decrease temperature and pressure, when pressure and temperature is down to 5.0MPa and 32-33 DEG C respectively in still, being exhausted decompression, decompression exhaust speed is first slow rear fast, exhaust velocity is 30-120ml/min, to still during pressure 0, open bleeder valve, obtain nano-TiO2Concentration is the functionalization TiO of the load CuPc of 7.14%2Dispersion liquid system, measures nano-TiO in dispersion liquid with nano particle size instrument2Size and distribution, function nano TiO2Aggregate particle mean size is 142.0nm.
According to polyvinylidene fluoride resin: dimethylacetamide solvent: polyvinylpyrrolidone additive 18:70:9 mix by weight, use machine mixer to stir, add 3 weight portions and utilize through the uniform above-mentioned TiO of ultrasonic cell disintegration instrument ultrasonic disperse2Dispersion liquid system solution, then adopts the mode of negative pressure to carry out deaeration, and the casting solution made after deaeration is positioned in batch can, 70 degree of insulations; It is the dimethyl acetylamide of 10:90 with mass ratio: water mixed solvent is that coagulating bath is circulated, then according to following method prepares nano modification lining-reinforced hollow-fibre membrane:
1) the fiber internal lining pipe pulled in fiber roller is passed sequentially through coating device and gel groove, be then around on wire drawing wheel;
2) opening wire-feed motor and receive silk machine, regulating the two rotating speed and make equipment run, the speed of the two is 15 ms/min, feed liquid is added in reactor, then pressurizes in reactor, makes the logical charge tube of feed liquid carry to coating device;
3) internal lining pipe is under the traction receiving silk machine, is coated with after feeding through coating device and enters coagulation bath, feed liquid generation immersion inversion of phases on internal lining pipe outer surface and gel sizing, loses flowability, forms film silk, is collected by wire drawing wheel;
4) a number of film silk will be collected and shear binding, and put into immersion 24h in tank, thoroughly displace solvent and additive;
5) film is dried process, both obtains described lining-reinforced hollow membrane;
Above-mentioned film is carried out following performance measurement:
1) average pore size using the obtained hollow-fibre membrane of solution-air and the double; two method of testing pore-size distribution analysis-e/or determining of liquid liquid is 0.2 micron, and internal diameter is 1.0 millimeters, and external diameter is 2.0 millimeters.
2) using the doughnut film-strength that universal tensile machine measures is 150N;
3) the described hollow-fibre membrane that use flux detector measures under 0.1MPa pressure pure water flux under 25 DEG C and 1 atmospheric pressure is 2500L/m2.h;
4) the described hollow-fibre membrane contact angle that dynamic contact angle analyzer measures is used to be sized to 38 degree;
Embodiment 2
Except polyvinylidene fluoride resin: dimethylacetamide solvent: except polyvinylpyrrolidone additive 15:75:5 by weight, all the other are with embodiment 1;
Test result is doughnut film-strength is 135N; Pure water flux is 2980LMH; Contact angle is sized to 40.2 degree.
Embodiment 3
Except adopting FePC and replacing CuPc, all the other are with embodiment 1;
Test result is doughnut film-strength is 152N; Pure water flux is 2510L/m2.h; Contact angle is sized to 38.2 degree.
Embodiment 4
It is the nano-TiO of 1:1 except adopting weight ratio2Dispersion liquid system replaces nano-TiO with Graphene2Outside dispersion liquid system, all the other are with embodiment 1;
Test result is doughnut film-strength is 155N; Pure water flux is 2580L/m2.h; Contact angle is sized to 36.5 degree.
Embodiment 5
It is the nano-TiO of 3:1 except adopting weight ratio2Dispersion liquid system replaces nano-TiO with Graphene2Outside dispersion liquid system, all the other are with embodiment 4;
Test result is doughnut film-strength is 146N; Pure water flux is 2560L/m2.h; Contact angle is sized to 36.8 degree.
Embodiment 6
It is the nano-TiO of 1:3 except adopting weight ratio2Dispersion liquid system replaces nano-TiO with Graphene2Outside dispersion liquid system, all the other are with embodiment 4;
Test result is doughnut film-strength is 147N; Pure water flux is 2540L/m2.h; Contact angle is sized to 45.0 degree.
As can be seen here, when adopting the nano functional masterbatch mixture with Graphene to replace nano functional masterbatch, its performance in doughnut film-strength, pure water flux and contact angle size etc. has further raising, and particularly the two is 1:1.
Comparative example 1:
Except being added without any nanometer of masterbatch, all the other are with embodiment 1;
Test result is doughnut film-strength is 145N; Pure water flux is 1480L/m2.h; Contact angle is sized to 82 degree.
Comparative example 2:
Except adding Al2O3Outside nano-particle, all the other are with embodiment 1;
Test result is doughnut film-strength is 143N; Pure water flux is 1890L/m2.h; Contact angle is sized to 70 degree.
Comparative example 2:
Except adding SiO2Outside nano-particle, all the other are with embodiment 1;
Test result is doughnut film-strength is 138N; Pure water flux is 1850L/m2.h; Contact angle is sized to 72 degree.
Comparative example 3:
Except adding ZrO2Outside nano-particle, all the other are with embodiment 1;
Test result is doughnut film-strength is 140N; Pure water flux is 1750L/m2.h; Contact angle is sized to 68 degree.
Comparative example 4
Except add oxide/carbon nanometer tube disclosed in CN201310014691.6 and graphene oxide with weight ratio for the mixture of 1:1, all the other are with embodiment 1;
Test result is doughnut film-strength is 150N; Pure water flux is 1950L/m2.h; Contact angle is sized to 45.2 degree.
Comparative example 5:
Except adding conventional TiO2Outside nano-particle, all the other are with embodiment 1;
Test result is doughnut film-strength is 147N; Pure water flux is 1880L/m2.h; Contact angle is sized to 55 degree.
As can be seen here, technical scheme, relative to the nano-particle that prior art is conventional, its performance in doughnut film-strength, pure water flux and contact angle size etc. has further improvement.
The above is only the preferred embodiments of the invention; it should be pointed out that, for those skilled in the art, under the premise without departing from the technology of the present invention principle; can also making some improvement and modification, these improve and modification also should be regarded as protection scope of the present invention.
Claims (8)
1. the polyvinylidene fluoride film modifiied through targeting potentiation nano-functional material, it is characterised in that described modified polyvinylidene fluoride film is made up of the following raw materials according with parts by weight:
Described solvent is N, at least one or multiple in N dimethyl acetamide, dimethylformamide and N-Methyl pyrrolidone;
Described porogen is nano functional masterbatch described in polyvinylpyrrolidone, Polyethylene Glycol, ethylene glycol or anhydrous Lithium chloride is the nano-TiO adopting following supercritical fluid processes to prepare2Dispersion liquid system:
By nano-TiO2Powder body, dehydrated alcohol, acetylacetone,2,4-pentanedione, triton x-100, and the mixed liquor of CuPc or FePC and N, N-dimethyl acetylamide joins in supercritical reaction still by the mass ratio of 1:100��1:0.03��0.1:0.03��0.1:0.003��0.01, wherein CuPc or FePC and N, N-dimethyl acetylamide are by weight stirring mixed processing at normal temperatures and pressures in advance for 1:2, reactor is heated to 30-100 DEG C, stirring and dissolving 15-60min, rotating speed 150-350rpm;CO by refrigeration to 5-8 DEG C2Being passed in reactor after the intensified pump supercharging of fluid, be under 100-350rpm in 31-100 DEG C of temperature and 7.14-10.0MPa pressure, speed of agitator, the supercritical time is not less than 5min; Then in coil pipe U-shaped in reactor, pass into 20-25 DEG C of recirculated cooling water and carry out decrease temperature and pressure, water velocity is 100-120ml/min, when in still, pressure and temperature is down to 5.2-4.8MPa and 36-32 DEG C respectively, it is exhausted decompression, exhaust velocity is 30-120ml/min, to still during pressure 1.0-0MPa, open bleeder valve, obtain nano-TiO2Dispersion liquid system.
2. polyvinylidene fluoride film according to claim 1, it is characterised in that described solvent is N, N dimethyl acetamide.
3. polyvinylidene fluoride film according to claim 1, it is characterised in that described porogen is polyvinylpyrrolidone or Polyethylene Glycol.
4. polyvinylidene fluoride film according to claim 1, it is characterised in that
Described modified polyvinylidene fluoride film is made up of the following raw materials according with parts by weight:
5. polyvinylidene fluoride film according to claim 1, it is characterised in that described nano functional masterbatch and Graphene are applied in polyvinylidene fluoride film with weight ratio for 3:1-1:3.
6. polyvinylidene fluoride film according to claim 6, it is characterised in that described nano functional masterbatch and Graphene are applied in polyvinylidene fluoride film with weight ratio for 1:1.
7. the polyvinylidene fluoride film prepared described in claim 1, it is characterised in that said method comprising the steps of:
(1) by pre-dispersed for nano functional masterbatch in a solvent, and utilize ultrasonic cell disintegration instrument to carry out ultrasonic disperse 1-3h;
(2) Kynoar and porogen are dissolved in a solvent, until completely dissolved, add the nano functional masterbatch being dispersed through of step (1), stir dispersed in the solution to it;
(3), after obtained solution being stirred 8-16h at 60-80 DEG C, take out negative pressure deaeration 1-6h, obtain the casting solution after deaeration;
(4) by described casting solution 15-30 DEG C, utilize under 30%-60% humidity dry-wet method to carry out spinning, spinning temperature is 50-80 DEG C; Entering coagulating bath film-forming by spinneret after being extruded by casting solution, temperature is 40-80 DEG C, and air bath is highly 10-40cm, and spinning speed is 10-30m/min, prepares the film of spinning; Described coagulation bath composition is the water of the solvent of 10-30,70-90 in parts by weight, and described solvent is N, N dimethyl acetamide, dimethylformamide and N-Methyl pyrrolidone, it is preferable that N, N dimethyl acetamide;
(5), after the film of spinning being soaked 12-24h in pure water, polyvinylidene fluoride film is prepared.
8. polyvinylidene fluoride film according to claim 1, it is characterised in that described polyvinylidene fluoride film is micro-filtration membrane, ultrafilter membrane or NF membrane.
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