CN108499374B - PVDF composite graphene filter element membrane and production process thereof - Google Patents
PVDF composite graphene filter element membrane and production process thereof Download PDFInfo
- Publication number
- CN108499374B CN108499374B CN201710105990.9A CN201710105990A CN108499374B CN 108499374 B CN108499374 B CN 108499374B CN 201710105990 A CN201710105990 A CN 201710105990A CN 108499374 B CN108499374 B CN 108499374B
- Authority
- CN
- China
- Prior art keywords
- pvdf
- filter element
- membrane
- pvp
- parts
- 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.)
- Active
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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/46—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
Abstract
The invention discloses a PVDF composite graphene filter element membrane and a production process thereof, which solve the problems that nano particles are poor in dispersibility in polyvinylidene fluoride and are easy to agglomerate, so that the porosity and the permeability of the prepared PVDF membrane are reduced to different degrees, and the technical scheme is characterized in that the PVDF composite graphene filter element membrane is prepared from the following raw materials in parts by mass: 30-45 parts of PVDF homopolymer, 60-75 parts of DMAC (dimethylacetamide), 1-2 parts of PVP (polyvinyl pyrrolidone) and 0.5-2.5 parts of modified graphene, and the components are added into a reaction kettle to prepare a spinning membrane and spin-form the spinning membrane, so that the effects of improving the dispersibility, hydrophilicity and mechanical strength of raw material components of the filter element are achieved, and the filter element has stable filtering precision.
Description
Technical Field
The invention relates to a PVDF filter element membrane, in particular to a PVDF composite graphene filter element membrane and a production process thereof.
Background
In recent 20 years, water pollution is increasingly serious due to lack of water resources, and in order to guarantee the safety of drinking water, a water outlet of a tap water pipe of a present household is connected with water purification equipment, and a large amount of harmful substances in water are filtered out through water purification and filtration.
The ultrafilter is a water purifying apparatus, and is different from other water purifying apparatuses in that it uses a filter element membrane. The filter element membrane is a microporous filter membrane with consistent pore size specification, and a membrane filtration method taking pressure difference as driving force is adopted for filtration.
Polyvinylidene fluoride (PVDF) has excellent heat resistance, mechanical property, radiation resistance and other characteristics, can be used as a material for manufacturing a filter element membrane, and the filter element membrane made of PVDF can filter bacteria and viruses and can retain trace elements necessary for human bodies. In order to improve the water purification effect of the water purifier, new requirements on the performance of the filter element membrane are continuously provided.
For example, a silver/TiO silver alloy is disclosed in patent publication No. CN102989329B2The modified PVDF ultrafiltration membrane comprises the following components in percentage by mass: 10-18% of polyvinylidene fluoride, 0.1-1.5% of pore-forming agent, and TiO20.5-6% of nano particles, 0.01-0.1% of silver-containing ion salt and 75-85% of solvent. The prepared PVDF membrane has the characteristics of high hydrophilicity, good catalytic activity and good antibacterial property. However, the nano particles have poor dispersibility in polyvinylidene fluoride and are easy to agglomerate, so that the porosity and the permeability of the prepared PVDF membrane are reduced to different degrees.
Disclosure of Invention
The first purpose of the invention is to provide a PVDF composite graphene filter core membrane with good dispersibility and high hydrophilicity.
The technical purpose of the invention is realized by the following technical scheme:
the PVDF composite graphene filter element membrane is prepared from the following raw materials in parts by mass: 30-45 parts of PVDF homopolymer, 60-75 parts of DMAC (dimethylacetamide), 1-2 parts of PVP (polyvinyl pyrrolidone) and 0.5-2.5 parts of modified graphene.
By adopting the technical scheme, the PVDF has excellent corrosion resistance, good mechanical property, good wear resistance, low friction coefficient, good aging resistance, high ultraviolet resistance, good electrical insulation and thermal stability, compared with PVDF copolymer, PVDF homopolymer has higher melting point and better temperature resistance, PVP can play a role in pore formation, and simultaneously, due to the hydrophilicity of PVP, PVDF can be modified, so that the PVDF filter membrane has better hydrophilicity, the anti-pollution capability of the filter membrane is improved, the service life of the filter membrane is prolonged, the structural strength of the filter membrane can be improved by adding the modified graphene, the average pore diameter of the membrane is reduced, meanwhile, the hydrophilicity of the membrane can be improved, the dispersibility and compatibility of graphene in PVDF are greatly improved after functionalization, the phenomenon of agglomeration of graphene is avoided, and the pore diameter of the prepared filter element membrane can be similar; DMAC is used as a solvent, has good solubility for each component, further improves the dispersibility, improves the dispersibility and the hydrophilicity of the filter element membrane prepared by the formula to a certain extent, and has good structural strength.
Preferably, the modified graphene is graphene oxide grafted PVP.
By adopting the technical scheme, after graphene is oxidized, the graphene is more active than graphene in property and has amphipathy, PVP is grafted on the graphene oxide, the dispersity of the graphene oxide is improved, the compatibility is also improved, and the graphene is prevented from being agglomerated in a PVDF system.
Preferably, the modified graphene further supports silver nanoparticles.
Through adopting above-mentioned technical scheme, the PVP that remains in the modified graphene can play the effect of reductant, makes silver ion can load better on the modified graphene, and the existence of nanometer silver particle can further improve the dispersibility of graphite alkene, strengthens the structural strength of filter element membrane, and simultaneously, nanometer silver particle still has the effect of disinfecting, has further optimized the functional of filter element membrane.
Preferably, the PVDF homopolymer has a weight average molecular weight of 60 to 65 ten thousand.
By adopting the technical scheme, if the weight average molecular weight of PVDF is too low, the mechanical strength of the PVDF is reduced, the prepared PVDF film is easy to become brittle, when the molecular weight of the PVDF homopolymer is too large, the viscosity of the PVDF is increased, difficulty is brought to molding, meanwhile, the dispersibility of the modified graphene and PVP in the PVDF can be reduced, the PVDF homopolymer with the weight average molecular weight in the range of 60-65 ten thousand has better mechanical strength, and meanwhile, the distribution of the weight average molecular weight is narrower, so that the processing and molding are facilitated.
Preferably, the PVP is prepared by blending PVP-K30 and PVP-K90 according to the mass ratio of 9: 1.
By adopting the technical scheme, the PVP-K30 with low molecular weight can play a plasticizing effect besides the effects of improving the hydrophilicity of PVP and forming holes, and the PVP-K90 with high molecular weight is added into PVP-K30 to play a certain slow-release role, so that the reaction speed of PVP-K30 in a solvent is slowed down, and the dispersion effect of PVP is improved.
The second purpose of the invention is to provide a production process of the PVDF composite graphene filter element membrane, which enables the deviation between the pore diameters of the filter element membrane to be small.
The technical purpose of the invention is realized by the following technical scheme:
a production process of a PVDF composite graphene filter core membrane comprises the following steps:
step1, putting PVDF homopolymer, DMAC, PVP and modified graphene into a reaction kettle, and setting the temperature to be 85-95 ℃ to prepare spinning solution;
step2, standing and defoaming the spinning solution, and spinning and forming to prepare tows;
step3, soaking the tows in an ethanol solution with the mass fraction of 10% for 10 minutes, and then putting the tows into a solidification tank to soak for 24-28 hours to obtain hollow fiber bundles with stable apertures;
and step4, airing the hollow fiber bundle to obtain the filter element membrane.
Through adopting above-mentioned technical scheme, mix the raw materials and can make the material disperse fast in reation kettle under 85~95 ℃, and the raw materials can not the direct contact air in reation kettle, DMAC moisture absorption alkalization has been avoided, and then spinning liquid solidifies in advance or rupture of membranes, after the defoaming of stewing, can make the tow surface level and smooth that makes, avoid wrinkling, after ethanol and coagulation bath soak, can stabilize the aperture, the difference in aperture between the filter core membrane of the same batch after making to dry is very little.
Preferably, the modified graphene is washed by dilute hydrochloric acid with the mass fraction of 4% for 4-5 times before being put into a reaction kettle.
Through adopting above-mentioned technical scheme, through dilute hydrochloric acid washing modified graphene can get rid of remaining PVP in the modified graphene in the grafting process, avoided the PVP content in whole component to increase too much and lead to the rupture of membranes, simultaneously, dilute hydrochloric acid remains after modified graphene surface adds reation kettle, can play the alkalization that the moisture absorption of neutralization DMAC caused, avoid this individual system alkalization to avoided PVDF not alkali-fast and insoluble in DMAC.
Preferably, the PVDF homopolymer is dried for 3 hours at 80-90 ℃ before being prepared and put into a reaction kettle.
By adopting the technical scheme, moisture in PVDF can be removed after the PVDF is dried, and the possibility of system alkalization caused by DMAC moisture absorption is further avoided.
Preferably, water and glycerin are added into the coagulation tank, and the mass ratio of the water to the glycerin is 4: 1.
By adopting the technical scheme, the PVDF tows are soaked in the glycerol, so that the effects of moisturizing and protecting the holes can be achieved, the situation that the holes shrink or collapse due to direct drying of the PVDF tows is avoided, and the reduction of the membrane flux is avoided.
In conclusion, the invention has the following beneficial effects:
1. according to the PVDF composite graphene filter element membrane, the modified graphene is added into a PVDF system, the structural strength of the PVDF filter element membrane is enhanced, the hydrophilicity of PVDF is enhanced by grafting PVP on graphene oxide, the dispersibility of the modified graphene in the PVDF system can be improved, then nano silver particles are loaded on the modified graphene, the graphene can be uniformly dispersed in the PVDF system through the nano silver particles and the PVP, meanwhile, the nano silver particles can be uniformly dispersed in the PVDF system, the agglomeration phenomenon is avoided, the filter element membrane after membrane forming has better pore-forming distribution, and therefore the filter element membrane has better flux;
2. the PVDF composite graphene filter element membrane further improves the structural strength of the filter element membrane through the dispersion of the nano silver particles, and meanwhile, the nano silver particles can promote the sterilization effect of the filter element membrane;
3. in the forming process of the PVDF composite graphene filter core membrane, firstly, modified graphene is washed by dilute hydrochloric acid, the dilute hydrochloric acid can wash out PVP (polyvinyl pyrrolidone) remained in a graphene oxide grafted PVP system after grafting PVP, and excessive PVP caused by repeatedly adding PVP into a PVDF composite membrane is avoided, so that membrane breakage caused by excessive bubbling amount is avoided; meanwhile, through cleaning with dilute hydrochloric acid, the modified graphene does not need to be purified for a long time, so that the manufacturing time of the modified graphene is saved; meanwhile, in the reaction process, because DMAC is easy to absorb water and deliquesce to cause system alkalization, the dilute hydrochloric acid remained in the modified graphene can play a role in neutralization, and the PVDF is prevented from being cured in advance in the standing and defoaming process due to the system alkalization.
Detailed Description
Preparing modified graphene:
1: graphene oxide grafted PVP:
(1) measuring 200mL of H2Adding 0.1g of graphene oxide into O, and performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid with the concentration of 0.5 mg/mL;
(2) weighing 0.2g of PVP, adding into the graphene oxide dispersion liquid obtained in the step (1), and fully stirring until the PVP is completely dissolved;
(3) weighing 0.2g of ascorbic acid, adding the ascorbic acid into the step (2), and fully stirring until the ascorbic acid is completely dissolved to obtain a mixed system;
(4) heating the mixed system obtained in the step (3) in an oil bath at 75 ℃ for 4h to obtain a graphene oxide grafted PVP solution;
2: loading nano silver particles:
(5) transferring the graphene oxide grafted PVP solution into a flask, filling nitrogen for 10min, and removing air in the flask;
(6) adding 0.01g of nano silver nitrate powder into the step (5), and stirring for 20 min;
(7) under the heating of water bath at 80 ℃, new 0.128mol/LNaBH is added dropwise4An aqueous solution;
(8) centrifuging the product obtained in the step (7), and taking the precipitate to obtain a modified graphene crude product;
(9) washing the modified graphene crude product with dilute hydrochloric acid with the weight percentage of 4%, taking the precipitate, washing the precipitate with dilute hydrochloric acid with the weight percentage of 4%, removing redundant PVP in the modified graphene crude product, repeating for 4 times, and drying the precipitate to obtain the modified graphene.
The weight average molecular weight of the selected PVDF homopolymer is between 60 and 65 ten thousand through rheological test.
Mixing glycerol and water at a mass ratio of 1: 4, and adding into a coagulation pool.
The first embodiment is as follows:
step1, putting the PVDF homopolymer into a drying box, and drying for 3 hours at 90 ℃;
step2, putting 45 parts of PVDF homopolymer, 75 parts of DMAC (dimethylacetamide), 301.8 parts of PVP-K and 2.5 parts of modified graphene into a reaction kettle, and setting the temperature to be 95 ℃ to prepare spinning solution;
step3, standing and defoaming the spinning solution, and spinning and forming to prepare tows;
step4, soaking the tows in an ethanol solution with the mass fraction of 10% for 10 minutes, and then putting the tows into a solidification pool to soak for 28 hours to obtain hollow fiber bundles with stable apertures;
and step5, airing the hollow fiber bundle to obtain the filter element membrane.
Example two:
step1, putting the PVDF homopolymer into a drying box, and drying for 3 hours at the temperature of 80 ℃;
step2, putting 30 parts of PVDF homopolymer, 60 parts of DMAC (dimethylacetamide), 300.9 parts of PVP-K900.1 and 0.5 part of modified graphene into a reaction kettle, and setting the temperature to be 85 ℃ to prepare spinning solution;
step3, standing and defoaming the spinning solution, and spinning and forming to prepare tows;
step4, soaking the tows in an ethanol solution with the mass fraction of 10% for 10 minutes, and then putting the tows into a solidification tank to soak for 24 hours to obtain hollow fiber bundles with stable apertures;
and step5, airing the hollow fiber bundle to obtain the filter element membrane.
Example three:
step1, putting the PVDF homopolymer into a drying oven, and drying for 3 hours at the temperature of 80-90 ℃;
step2, putting 45 parts of PVDF homopolymer, 75 parts of DMAC (dimethylacetamide), 75 parts of PVP-K300.9 parts of PVP-K900.1 and 2.0 parts of modified graphene into a reaction kettle, and setting the temperature to be 85 ℃ to prepare spinning solution;
step3, standing and defoaming the spinning solution, and spinning and forming to prepare tows;
step4, soaking the tows in an ethanol solution with the mass fraction of 10% for 10 minutes, and then putting the tows into a solidification pool to soak for 28 hours to obtain hollow fiber bundles with stable apertures;
and step5, airing the hollow fiber bundle to obtain the filter element membrane.
Example four:
step1, putting the PVDF homopolymer into a drying box, and drying for 3 hours at 85 ℃;
step2, putting 45 parts of PVDF homopolymer, 60 parts of DMAC (dimethylacetamide), 301.8 parts of PVP-K and 1.5 parts of modified graphene into a reaction kettle, and setting the temperature to be 85 ℃ to prepare spinning solution;
step3, standing and defoaming the spinning solution, and spinning and forming to prepare tows;
step4, soaking the tows in an ethanol solution with the mass fraction of 10% for 10 minutes, and then putting the tows into a solidification pool to soak for 28 hours to obtain hollow fiber bundles with stable apertures;
and step5, airing the hollow fiber bundle to obtain the filter element membrane.
Example five:
step1, putting the PVDF homopolymer into a drying oven, and drying for 3 hours at the temperature of 80-90 ℃;
step2, putting 30 parts of PVDF homopolymer, 75 parts of DMAC (dimethylacetamide), 301.8 parts of PVP-K and 2.0 parts of modified graphene into a reaction kettle, and setting the temperature to be 90 ℃ to prepare spinning solution;
step3, standing and defoaming the spinning solution, and spinning and forming to prepare tows;
step4, soaking the tows in an ethanol solution with the mass fraction of 10% for 10 minutes, and then putting the tows into a solidification pool to soak for 28 hours to obtain hollow fiber bundles with stable apertures;
and step5, airing the hollow fiber bundle to obtain the filter element membrane.
Example six:
step1, putting the PVDF homopolymer into a drying box, and drying for 3 hours at 90 ℃;
step2, putting 35 parts of PVDF homopolymer, 75 parts of DMAC (dimethylacetamide), 75 parts of PVP-K300.9 parts of PVP-K900.1 parts and 1.5 parts of modified graphene into a reaction kettle, and setting the temperature to be 85 ℃ to prepare spinning solution;
step3, standing and defoaming the spinning solution, and spinning and forming to prepare tows;
step4, soaking the tows in an ethanol solution with the mass fraction of 10% for 10 minutes, and then putting the tows into a solidification pool to soak for 28 hours to obtain hollow fiber bundles with stable apertures;
and step5, airing the hollow fiber bundle to obtain the filter element membrane.
Filter element membranes were prepared according to the six groups of examples above and tested as follows:
average pore diameter (μm)/maximum pore diameter (μm): shearing a section of filter element membrane, firstly using absolute ethyl alcohol, then using deionized water to wash off dust on the surface of the membrane, drying in vacuum at 60 ℃ until the membrane is completely dehydrated, quenching by using liquid nitrogen to obtain a membrane section, sputtering by using an ion sputtering instrument, plating a layer of metal membrane, shearing a sample with a proper length, fixing the sample on a sample table, observing and photographing by using an electron microscope, measuring and counting holes on the picture, and calculating the average aperture and the maximum aperture;
contact angle (°): testing the contact angle between the water drop and the surface of the filter element membrane by using a contact angle tester;
initial pure water flux (L.m)-2·h-1): soaking the filter element membrane in pure water for 2h, then taking out, compacting a membrane water flux testing device filled with deionized water for 30min by using nitrogen, recording the permeation quantity of water passing through the membrane within 1 min, and calculating the initial pure water flux according to the pure water flux which is the effective membrane area/permeation time;
and (3) anti-pollution test:
(1) preparing 0.5g/L bovine serum albumin stock solution, measuring the absorbance value of the stock solution at a 280nm wavelength by using a spectrophotometer, compacting a filter element membrane for 30min at room temperature, measuring the absorbance value of the permeation solution filtered by the filter element membrane at the 280nm wavelength, and calculating the retention rate of the bovine serum albumin stock solution according to the retention rate (1-absorbance value of the permeation solution/absorbance value of the stock solution) · 100%;
(2) pure water flux (L.m) after washing-2·h-1): cleaning a filter element membrane filtered with bovine serum albumin stock solution, soaking the cleaned filter element membrane in pure water for 2 hours, taking out, compacting membrane water flux testing equipment filled with deionized water for 30 minutes by using nitrogen, recording the permeation quantity of water passing through the membrane within 1 minute, and calculating the pure water flux after cleaning according to the pure water flux which is the effective membrane area/permeation time;
tensile strength (Mpa): the tensile strength of the dry film of the filter element film was measured at a mechanical tensile rate of 2mm/min using a universal electronic tensile tester.
The test results are given in the following table:
by comparison in the table above, example five was selected as the most preferred example for comparison with the comparative sample of the comparative example described below.
Comparative example one:
comparative example one is a filter element membrane obtained by washing the modified graphene in example five without diluted hydrochloric acid.
Comparative example two:
comparative example two is a filter element membrane made from PVP-K30 selected for the PVP used in example five.
Comparative example three:
comparative example three is a filter element membrane made from PVP-K90 selected for the PVP used in example five.
Comparative example four:
comparative example four is a filter element membrane made from PVP-K60 selected for the PVP used in example five.
Comparative example five:
and the fifth comparative example is a filter element membrane prepared by non-grafting PVP on the modified graphene in the fifth example.
Comparative example six:
and the sixth comparative example is a filter element film prepared by the modified graphene in the fifth example without coating nano silver particles.
Comparative example seven:
comparative example seven is a commercially available PVDF filter element membrane.
Test methods were as above, with the test results shown in the following table:
compared with the filter core membranes manufactured in the market and the comparative example, the PVDF composite graphene filter core membrane manufactured by the formula has the advantages that the average pore diameter is 0.01 mu m, the filtering precision is better, the deviation between the adjacent pore diameters of the filter core is smaller, and the consistency of the pore diameters is high by comparing the maximum pore diameter with the average pore diameter; the contact angle is in the range of 25-35 degrees, and the pure water flux is 600 L.m-2·h-1Above, have splendid hydrophilicity, and the pure water flux of retesting after the entrapment rate test of bovine serum albumin stoste, it is very little to find its decline rate, and simultaneously, this filter core membrane still has better tensile strength, has prolonged the life of filter core.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (8)
1. The PVDF composite graphene filter element membrane is characterized in that the preparation raw materials comprise the following components in parts by mass: 30-45 parts of PVDF homopolymer, 60-75 parts of DMAC (dimethylacetamide), 1-2 parts of PVP (polyvinyl pyrrolidone) and 0.5-2.5 parts of modified graphene; the modified graphene is graphene oxide grafted PVP.
2. The PVDF composite graphene filter core membrane according to claim 1, wherein the modified graphene is further loaded with nano silver particles.
3. The PVDF composite graphene filter element membrane as claimed in claim 1, wherein the weight average molecular weight of the PVDF homopolymer is 60-65 ten thousand.
4. The PVDF composite graphene filter element membrane as claimed in claim 1, wherein the PVP is formed by blending PVP-K30 and PVP-K90 according to a mass ratio of 9: 1.
5. The production process of the PVDF composite graphene filter element membrane according to any one of claims 1 to 4, characterized by comprising the following steps:
step1, putting PVDF homopolymer, DMAC, PVP and modified graphene into a reaction kettle, and setting the temperature to be 85-95 ℃ to prepare spinning solution;
step2, standing and defoaming the spinning solution, and spinning and forming to prepare tows;
step3, soaking the tows in an ethanol solution with the mass fraction of 10% for 10 minutes, and then putting the tows into a solidification tank to soak for 24-28 hours to obtain hollow fiber bundles with stable apertures;
and step4, airing the hollow fiber bundle to obtain the filter element membrane.
6. The production process of the PVDF composite graphene filter element membrane according to claim 5, wherein the modified graphene is washed by dilute hydrochloric acid with a mass fraction of 4% for 4-5 times before being put into a reaction kettle.
7. The production process of the PVDF composite graphene filter core membrane according to claim 5, wherein the PVDF homopolymer is dried at 80-90 ℃ for 3h before being prepared and put into a reaction kettle.
8. The production process of the PVDF composite graphene filter core membrane as claimed in claim 5, wherein water and glycerol are added into the coagulation tank, and the mass ratio of the water to the glycerol is 4: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710105990.9A CN108499374B (en) | 2017-02-24 | 2017-02-24 | PVDF composite graphene filter element membrane and production process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710105990.9A CN108499374B (en) | 2017-02-24 | 2017-02-24 | PVDF composite graphene filter element membrane and production process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108499374A CN108499374A (en) | 2018-09-07 |
| CN108499374B true CN108499374B (en) | 2020-06-05 |
Family
ID=63372815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710105990.9A Active CN108499374B (en) | 2017-02-24 | 2017-02-24 | PVDF composite graphene filter element membrane and production process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108499374B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110038454B (en) * | 2019-04-25 | 2020-12-04 | 浙江大学 | High-strength and high-water-flux graphene modified PVDF (polyvinylidene fluoride) ultra-micro filter membrane and preparation method thereof |
| CN110280142A (en) * | 2019-06-24 | 2019-09-27 | 南京龙源环保有限公司 | Silver-colored graphene oxide polyvinylidene fluoride hollow fiber ultrafiltration membrane of a kind of load and preparation method thereof |
| CN112626711A (en) * | 2020-11-16 | 2021-04-09 | 广西中科鼎新产业技术研究院有限公司 | Hydrophilic nanofiber membrane and preparation method thereof |
| CN113813799A (en) * | 2021-09-13 | 2021-12-21 | 上海海若环境集团有限公司 | Preparation method of PVDF ultrafiltration membrane with polyester lining |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102688707A (en) * | 2012-05-23 | 2012-09-26 | 哈尔滨工业大学 | Preparation method for graphene oxide/polyvinylidene fluoride composite ultrafiltration membrane |
| CN104353366B (en) * | 2014-11-10 | 2016-08-17 | 东华大学 | A kind of polymeric film with antifouling and antibiosis function and preparation method thereof |
-
2017
- 2017-02-24 CN CN201710105990.9A patent/CN108499374B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108499374A (en) | 2018-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108499374B (en) | PVDF composite graphene filter element membrane and production process thereof | |
| CN106215720B (en) | Preparation method of graphene quantum dot doped organic solvent resistant ultrafiltration membrane, prepared ultrafiltration membrane and application of ultrafiltration membrane | |
| CN102160967B (en) | Lining-reinforced hollow fiber membrane tube as well as preparation device and preparation method thereof | |
| CN113828162B (en) | Preparation method of sustainable hydrophilic modified polyvinylidene fluoride hollow membrane | |
| CN103394293B (en) | A kind of preparation method of hydrophilia polyvinylidene fluoride hollow fiber membrane | |
| CN103170260B (en) | Modified nanometer titanium dioxide based preparation process of hollow ultrafiltration membrane fiber | |
| CN103143268B (en) | The preparation method of polyvinylidene fluoride/polyurethane/polyvinyl chloride blend hollow fiber separation membrane | |
| CN109012214B (en) | Method for preparing high-permeability ultrafiltration membrane based on chemical pore-forming | |
| CN104383818A (en) | Composite microporous diaphragm, preparation method and application thereof | |
| CN107694356B (en) | beta-CD/HNTs (beta-CD/HNTs) blended polyvinylidene fluoride film and preparation method thereof | |
| CN110280148B (en) | Preparation method of polyvinylidene fluoride ultrafiltration membrane modified by hydrophilic graphene | |
| CN106139928A (en) | Endotoxin filter membrane and manufacture method thereof in a kind of dialysis solution water | |
| CN113318611B (en) | Hollow fiber ultrafiltration membrane with lasting high pollution resistance and preparation method thereof | |
| CN112619451B (en) | Preparation method of hydrophilic polytetrafluoroethylene hollow fiber microfiltration membrane | |
| JP5633128B2 (en) | Manufacturing method of separation membrane | |
| CN113041847A (en) | Molybdenum disulfide oxide composite film and preparation method thereof | |
| CN111359458A (en) | Molybdenum disulfide oxide modified flat nanofiltration membrane as well as preparation method and application thereof | |
| CN112191108B (en) | Preparation method of polyvinylidene fluoride hollow fiber ultrafiltration membrane capable of intercepting heavy metal ions | |
| CN103143267B (en) | The preparation method of polysulfone/polyurethane/polyvinyl chloride blend hollow fiber separation membrane | |
| CN111036087B (en) | Anti-pollution hollow fiber ultrafiltration membrane and preparation method thereof | |
| KR20220113961A (en) | Separator and manufacturing method of the separation membrane | |
| CN110935324A (en) | A kind of Ni (OH)2Preparation method of (E) -GO/PES (polyether sulfone) blended ultrafiltration membrane | |
| CN103464002A (en) | Preparation method of composite hollow fiber membrane | |
| CN115558125B (en) | Composite solvent and preparation method and application thereof | |
| CN115738743B (en) | Method for preparing durable high-performance ultrafiltration membrane based on supermolecule assembly reinforced blending method |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210508 Address after: CiDong Industrial Zone, Cixi City, Ningbo City, Zhejiang Province Patentee after: NINGBO DUKANG CERAMICS Ltd. Address before: CiDong Industrial Zone, Longshan Town, Cixi City, Ningbo City, Zhejiang Province Patentee before: NINGBO QINGSHUIFANG ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right |