CN105413494A - High-performance lyophilic PVDF/GO-lysine composite membrane - Google Patents
High-performance lyophilic PVDF/GO-lysine composite membrane Download PDFInfo
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- CN105413494A CN105413494A CN201610000907.7A CN201610000907A CN105413494A CN 105413494 A CN105413494 A CN 105413494A CN 201610000907 A CN201610000907 A CN 201610000907A CN 105413494 A CN105413494 A CN 105413494A
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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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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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
- B01D69/12—Composite membranes; Ultra-thin membranes
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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 discloses a high-performance lyophilic PVDF/GO-lysine composite membrane, and a preparation method and application thereof. The method includes the steps of modifying graphene oxide (GO) through lysine in deionized water under the existence of DCC to prepare a GO-lysine compound, modifying a PVDF original membrane in NMP with GO-lysine as an additive, and conducting cooling, defoaming, membrane wiping, solidifying and washing to prepare the high-performance lyophilic PVDF/GO-lysine composite membrane. The hydrophilic performance and the antifouling performance of the PVDF/GO-lysine composite membrane are both greatly improved, the PVDF/GO-lysine composite membrane can be used for seawater treatment, brackish water desalination, water filtration and purification and the like, the problem that a traditional PVDF membrane is prone to hydrophobic substance pollution is effectively solved, application prospects of the PVDF membrane is further widened, and the PVDF membrane is simple in preparation method and easy to implement.
Description
Technical field
The invention belongs to polymeric membrane for separation technical field of modification, be specifically related to a kind of high-performance hydrophilic PVDF/GO-lysine composite membrane and preparation method thereof and application.
Background technology
Kynoar (PVDF) film, owing to having excellent chemical stability, heat endurance and outstanding mechanical performance, makes it be widely used in various water treatment field, as sanitary sewage disposal, Industrial Wastewater Treatment etc. as the typical ultrafiltration membrane material of one.But PVDF is a kind of hydrophobic material, this makes pvdf membrane easily be subject to the pollution of the organic substances such as protein when water treatment, and the service life of film is shortened greatly, also reduces the selectivity of film simultaneously.Research shows, the hydrophily improving film effectively suppresses memebrane protein to pollute.At present, the hydrophilic improving countermeasure of pvdf membrane mainly blending and modifying.
Graphene oxide (GO) is the product of powdered graphite after chemical stripping, and it has single atomic layer, and its surface has more hydroxyl, carboxyl and epoxy-functional, facilitates further functionalization, makes it in water treatment, have huge application prospect; Meanwhile, GO itself also has good chemical stability, hydrophily, antifouling property, biocompatibility and mechanical performance, is the functionalization material with very large application potential.
Lysine (lysine) is a kind of biomaterial, waits hydrophilic functional group, obtain extensive use at present in a lot of fields in its structure containing carboxyl and amino.
Summary of the invention
High-performance hydrophilic PVDF/GO-lysine composite membrane that the object of the present invention is to provide a kind of GO-lysine modification and preparation method thereof and application.It is the former film of additive agent modified PVDF with GO-lysine, the hydrophilicity of gained PVDF/GO-lysine composite membrane and antifouling property are all greatly improved, can be used for Seawater Treatment, brackish water desalination, water filtration purification etc., can effectively increase water quality, and solve conventional P VDF film easily by the problem that lyophobic dust pollutes, expand the application prospect of pvdf membrane further.
For achieving the above object, the present invention adopts following technical scheme:
A kind of high-performance hydrophilic PVDF/GO-lysine composite membrane, it is that additive carries out modification to pvdf membrane with GO-lysine, and obtained have the hydrophilic PVDF/GO-lysine composite membrane of high-performance.
Its preparation method comprises the following steps:
1) join in deionized water by graphene oxide GO powder, 200W ultrasonic process 2h, then adds lysine lysine and dehydrated reagent DCC(N, N '-dicyclohexylcarbodiimide), 60-70 DEG C of lower magnetic force stirs 24h; After reaction terminates, by product through dialysis treatment, freeze-drying, obtain GO-lysine compound;
2) by GO-lysine compound, PVDF and pore former PVP(polyvinylpyrrolidone) join NMP(N-methyl pyrrolidone) in, stir 24h at 50-70 DEG C, obtain homogeneous casting solution;
3) by casting solution through cooling, after deaeration process, with scraper knifing on glass plate, then it is placed 15min in the deionized water coagulating bath of 40 ~ 60 DEG C, then composite membrane is taken out from coagulating bath, use washed with de-ionized water 48h, naturally dry and obtain PVDF/GO-lysine composite membrane.
Graphene oxide GO powder 0.2-0.5g is added in every 50mL deionized water, lysine lysine0.7-1.5g, DCC0.03-0.08g in step 1).
Step 2) in be 100% by raw material weight percentage sum, the proportioning of each raw material is: PVDF11-17%, GO-lysine compound 2-8%, PVP6%, NMP75%.
Described high-performance hydrophilic PVDF/GO-lysine composite membrane can be used for Seawater Treatment in water treatment field, brackish water desalination and water filtration purification etc.
The hydrophobicity of conventional P VDF film is unfavorable for its application in aqueous phase separation system, this mainly due to: its hydrophobic performance makes to need very high pressure that water just can be made by pvdf membrane in operation, and pure water flux is low; Simultaneously in the organic pollution surface that is easily adsorbed onto pvdf membrane and hole, make Pore Blocking, cause fouling membrane, and then cause the shortening in flux depression and service life.
Its hydrophilicity of PVDF/GO-lysine composite membrane of GO-lysine modification and antifouling property are all greatly improved, thus make it in water pollutions process and filtration etc., have better application performance, effectively can reduce the enrichment of protein on film surface and absorption simultaneously, its antifouling property is strengthened.
Therefore, compared with prior art, high-performance hydrophilic PVDF/GO-lysine composite membrane that the present invention obtains, remain on the one hand GO mechanical property good, corrosion-resistant, to advantages such as better heat stability, simultaneously, due to adding of lysine, improve the dispersion stabilization of GO in water or organic solvent; On the other hand, because GO-lysine has more hydrophilic functional groups, in process prepared by composite membrane, can migrate to the surface of film, the hydrophilicity of composite membrane and antifouling property are greatly improved, and recycling performance is higher.
Accompanying drawing explanation
Fig. 1 is the contact angle size situation over time of the PVDF/GO-lysine composite membrane that different proportion GO-lysine modification obtains;
Fig. 2 is that the PVDF/GO-lysine composite membrane that obtains of different proportion GO-lysine modification is to the Static Adsorption situation of BSA;
Fig. 3 is the dynamic antifouling property of the PVDF/GO-lysine composite membrane that different proportion GO-lysine modification obtains;
Wherein, M0 is the former film of PVDF, and M1 is 2%GO-lysine modification, and M2 is 4%GO-lysine modification, and M3 is 6%GO-lysine modification, and M4 is 8%GO-lysine modification.
Detailed description of the invention
More being convenient to make content of the present invention understand, below in conjunction with detailed description of the invention, technical solutions according to the invention are described further, but the present invention being not limited only to this.
embodiment 1
1) join in 50mL deionized water by 0.2 graphene oxide powder, 200W ultrasonic process 2h, then adds 0.7g lysine and 0.03gDCC, and 65 DEG C of lower magnetic forces stir 24h; After reaction terminates, by product through dialysis treatment, freeze-drying, obtain GO-lysine compound;
2) 0.8gGO-lysine compound, 6.8gPVDF, 2.4gPVP are joined in 30gNMP, at 50 DEG C, stir 24h, obtain homogeneous casting solution;
3) by casting solution through cooling, after deaeration process, with scraper knifing on glass plate, then it is placed 15min in the deionized water coagulating bath of 40 DEG C, again composite membrane is taken out from coagulating bath, use washed with de-ionized water 48h, naturally dry, the high-performance hydrophilic PVDF/GO-lysine composite membrane of obtained 2%GO-lysine modification, is designated as M1.
embodiment 2
1) join in 50mL deionized water by 0.3g graphene oxide powder, 200W ultrasonic process 2h, then adds 1.0g lysine and 0.04gDCC, and 65 DEG C of lower magnetic forces stir 24h; After reaction terminates, by product through dialysis treatment, freeze-drying, obtain GO-lysine compound;
2) 1.6gGO-lysine compound, 6.0gPVDF, 2.4gPVP are joined in 30gNMP, at 60 DEG C, stir 24h, obtain homogeneous casting solution;
3) by casting solution through cooling, after deaeration process, with scraper knifing on glass plate, then it is placed 15min in the deionized water coagulating bath of 50 DEG C, again composite membrane is taken out from coagulating bath, use washed with de-ionized water 48h, naturally dry, the high-performance hydrophilic PVDF/GO-lysine composite membrane of obtained 4%GO-lysine modification, is designated as M2.
embodiment 3
1) join in 50mL deionized water by 0.4g graphene oxide powder, 200W ultrasonic process 2h, then adds 1.2g lysine and 0.05gDCC, and 65 DEG C of lower magnetic forces stir 24h; After reaction terminates, by product through dialysis treatment, freeze-drying, obtain GO-lysine compound;
2) 2.4gGO-lysine compound, 5.2gPVDF, 2.4gPVP are joined in 30gNMP, at 60 DEG C, stir 24h, obtain homogeneous casting solution;
3) by casting solution through cooling, after deaeration process, with scraper knifing on glass plate, then it is placed 15min in the deionized water coagulating bath of 60 DEG C, again composite membrane is taken out from coagulating bath, use washed with de-ionized water 48h, naturally dry, the high-performance hydrophilic PVDF/GO-lysine composite membrane of obtained 6%GO-lysine modification, is designated as M3.
embodiment 4
1) join in 50mL deionized water by 0.5g graphene oxide powder, 200W ultrasonic process 2h, then adds 1.5g lysine and 0.08gDCC, and 65 DEG C of lower magnetic forces stir 24h; After reaction terminates, by product through dialysis treatment, freeze-drying, obtain GO-lysine compound;
2) 3.2gGO-lysine compound, 4.4gPVDF, 2.4gPVP are joined in 30gNMP, at 70 DEG C, stir 24h, obtain homogeneous casting solution;
3) by casting solution through cooling, after deaeration process, with scraper knifing on glass plate, then it is placed 15min in the deionized water coagulating bath of 50 DEG C, again composite membrane is taken out from coagulating bath, use washed with de-ionized water 48h, naturally dry, the high-performance hydrophilic PVDF/GO-lysine composite membrane of obtained 8%GO-lysine modification, is designated as M4.
Fig. 1 is the contact angle size situation over time of the PVDF/GO-lysine composite membrane that different proportion GO-lysine modification obtains.As can be seen from Figure 1, the contact angle of the former film M0 of PVDF is about 102 °, and after GO-lysine modification, the initial contact angle of Modified Membrane is obviously reduced to about 80 °, illustrates that the hydrophilicity of PVDF/GO-lysine composite membrane of the present invention is significantly improved; And along with the prolongation of time, the contact angle decrease speed of PVDF/GO-lysine film is faster than the former film of PVDF, and especially M2, is reduced to 25 ° after 8s.
Fig. 2 is that the PVDF/GO-lysine composite membrane that obtains of different proportion GO-lysine modification is to the Static Adsorption situation of BSA.As can be seen from Figure 2, the BSA adsorbance of PVDF/GO-lysine composite membrane is starkly lower than the former film of PVDF, and along with the increase of GO-lysine mass fraction in PVDF/GO-lysine composite membrane, BSA adsorbance reduces gradually; For M4, adsorbance is about 4mg/g; Illustrate that the static antifouling property of PVDF/GO-lysine composite membrane of the present invention significantly improves.
Fig. 3 is the dynamic antifouling property of the PVDF/GO-lysine composite membrane that different proportion GO-lysine modification obtains.As can be seen from Figure 3, the water flux of PVDF/GO-lysine composite membrane is apparently higher than the former film of PVDF, and dynamic anti-BSA adsorption capacity is better than the former film of PVDF.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (5)
1. high-performance hydrophilic PVDF/GO-lysine composite membrane, is characterized in that: be that additive carries out modification to pvdf membrane with GO-lysine, and obtained have the hydrophilic PVDF/GO-lysine composite membrane of high-performance.
2. a preparation method for high-performance hydrophilic PVDF/GO-lysine composite membrane as claimed in claim 1, is characterized in that: comprise the following steps:
1) graphene oxide powder is joined in deionized water, 200W ultrasonic process 2h, then add lysine and dehydrated reagent DCC, 60-70 DEG C of lower magnetic force stirring 24h; After reaction terminates, by product through dialysis treatment, freeze-drying, obtain GO-lysine compound;
2) GO-lysine compound, PVDF and pore former PVP are joined in NMP, at 50-70 DEG C, stir 24h, obtain homogeneous casting solution;
3) by casting solution through cooling, after deaeration process, with scraper knifing on glass plate, then it is placed 15min in the deionized water coagulating bath of 40 ~ 60 DEG C, then composite membrane is taken out from coagulating bath, use washed with de-ionized water 48h, naturally dry and get final product.
3. the preparation method of high-performance hydrophilic PVDF/GO-lysine composite membrane according to claim 2, is characterized in that: add graphene oxide powder 0.2-0.5g, lysine 0.7-1.5g, DCC0.03-0.08g in every 50mL deionized water in step 1).
4. the preparation method of high-performance hydrophilic PVDF/GO-lysine composite membrane according to claim 2, it is characterized in that: step 2) in be 100% by raw material weight percentage sum, the proportioning of each raw material is: PVDF11-17%, GO-lysine compound 2-8%, PVP6%, NMP75%.
5. the high-performance hydrophilic PVDF/application of GO-lysine composite membrane in water treatment as claimed in claim 1.
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Cited By (5)
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| CN105921031A (en) * | 2016-05-15 | 2016-09-07 | 高学理 | Carboxylic oxidized graphene and method for modifying organic release film by means of same |
| CN109865438A (en) * | 2017-12-01 | 2019-06-11 | 俞小峰 | A kind of preparation method of antibacterial stable type nanofiltration membrane material |
| WO2019143299A1 (en) * | 2018-01-18 | 2019-07-25 | Antony Prince James Selvaraj | Hyper-branched compounds, synthesis and uses thereof |
| CN110252154A (en) * | 2019-07-16 | 2019-09-20 | 华侨大学 | A kind of graphene oxide/graphite phase carbon nitride composite membrane preparation method of glycine modification |
| CN110559877A (en) * | 2019-09-26 | 2019-12-13 | 哈尔滨工程大学 | Preparation method and application of hydrophilic and antibacterial dual-modified ultrafiltration membrane |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105921031A (en) * | 2016-05-15 | 2016-09-07 | 高学理 | Carboxylic oxidized graphene and method for modifying organic release film by means of same |
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| CN110252154A (en) * | 2019-07-16 | 2019-09-20 | 华侨大学 | A kind of graphene oxide/graphite phase carbon nitride composite membrane preparation method of glycine modification |
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| CN110559877A (en) * | 2019-09-26 | 2019-12-13 | 哈尔滨工程大学 | Preparation method and application of hydrophilic and antibacterial dual-modified ultrafiltration membrane |
| CN110559877B (en) * | 2019-09-26 | 2022-01-07 | 哈尔滨工程大学 | Preparation method and application of hydrophilic and antibacterial dual-modified ultrafiltration membrane |
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