CN103120902A - Preparation method of carbon nanotube nanosilica co-modified polyvinyl alcohol composite ultra-filtration membrane - Google Patents
Preparation method of carbon nanotube nanosilica co-modified polyvinyl alcohol composite ultra-filtration membrane Download PDFInfo
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- CN103120902A CN103120902A CN2012104526731A CN201210452673A CN103120902A CN 103120902 A CN103120902 A CN 103120902A CN 2012104526731 A CN2012104526731 A CN 2012104526731A CN 201210452673 A CN201210452673 A CN 201210452673A CN 103120902 A CN103120902 A CN 103120902A
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Abstract
The invention discloses a preparation method of a carbon nanotube nanosilica co-modified polyvinyl alcohol composite ultra-filtration membrane. The preparation method comprises the following steps of: adding a certain amount of carboxylated carbon nanotubes and nanosilica which are dispersed by a surfactant, to a casting membrane solution by adopting polyvinyl alcohol as a membrane substrate material; and preparing the membrane by adopting polyethylene glycol as a pore-foaming agent through an immersion-precipitation phase transformation process. The prepared membrane not only has the hydrophily of the polyvinyl alcohol to achieve strong anti-pollution capacity, but also keeps the strength and toughness of inorganic materials to make up the defects of low strength and inability of resisting pressure of the polyvinyl alcohol wet membrane. The composite ultra-filtration membrane has strong anti-pollution capacity, high water flux and better retaining characteristic, can be repeatedly used and is long in service life.
Description
Technical field
The present invention relates to a kind of preparation method of the milipore filter for separating of technique, particularly a kind of CNT, the nano silicon preparation method of modified polyvinylalcohol composite hyperfiltration membrane altogether.
Background technology
Ultrafiltration is as sieving, and (0.1～1.6MPa), it only allows solvent and sees through less than the solute of membrane aperture, and stops the solute greater than membrane aperture to pass through, with purification, the separation and concentrated of completing solution under certain pressure.Ultra-filtration process has following main feature: can separate under normal temperature and low pressure, thereby energy consumption be low without the variation between the phase border (1), is about 1/ 2 of evaporation or freezing～1/ 5; (2) equipment volume is little, and is simple in structure, and investment cost is low; (3) technique is simple, easy operating; (4) variation of matter does not occur in material in the concentrating and separating process, thereby is suitable for protecting the processing of flavor and heat-sensitive substance; (5) the material classification of different relative molecular masses can be separated; (6) in use come off without any impurity, guarantee that ultrafiltrate is pure.External hyperfiltration technique is used early in the field of the film heavy contamination such as dairy husbandry, Juice Industry, biotechnology, also more successful, proportion is very large; And China is due to the technical merit and the larger gap of external existence of film; Add the reasons such as small scale of enterprise, applicable cases is just in time opposite, and application mainly concentrates on film and pollutes lighter field, pollutes heavy industry at film and basically is not applied.
Because the structure of polyvinyl alcohol (PVA) is strict line style, compound with regular structure, so stable chemical nature, the mechanical strength of material is high; The hydrogen bond that exists between molecule makes it that enough heat endurances be arranged; It is highly hydrophilic that hydroxyl on strand has it, is one of material that in existing macromolecular material, hydrophily is fabulous.Because PVA has highly hydrophilic, good stain resistance and film forming, and cheap, therefore, very suitable film material as osmotic evaporation film, reverse osmosis membrane, NF membrane, dialyser, enzyme membrane, gas separation membrane, microcapsule membrane etc., existing many relevant research and development reports, but PVA is also less as the research and development of milipore filter film material.
Pure PVA basement membrane is easy swelling, wet film intensity difference, not withstand voltage in water, has limited to a great extent its industrial applications, must carry out modification to it so will obtain the PVA milipore filter that intensity is good, water-swellable is low.Common method of modifying is to introduce the second component, can with the PVA molecule in hydroxyl form covalent bond or hydrogen bond, make it change into water-fast group, and then improve the water resistance of film, obtain high-intensity PVA milipore filter.In recent years, organic-inorganic nano particle composite membrane combines the characteristics of organic polymer and inorganic material, becomes the focus of membrane science research.Studies show that in a large number, add inorganic nano-particle in organic basement membrane, can increase mechanical strength and the life-span of film, suppress the formation of macroporous structure, thereby make film have excellent permeance property, can also increase the Film conductivity energy simultaneously.
Summary of the invention
The purpose of this invention is to provide a kind of CNT, the nano silicon preparation method of modified polyvinylalcohol composite hyperfiltration membrane altogether, prepared this composite hyperfiltration membrane has stronger contamination resistance, high water flux and holds back preferably characteristic, but Reusability, long service life.
In order to realize above goal of the invention, the present invention by the following technical solutions: a kind of CNT, nano silicon be the preparation method of modified polyvinylalcohol composite hyperfiltration membrane altogether, comprises the following steps:
(1) prepare raw material by following weight proportion: 100 parts of polyvinyl alcohol; 1～6 part of CNT; 1～4 part of nano silicon, 10～25 parts of polyethylene glycol; 30～40 parts of saturated metabisulfite solutions; 1～6 part of lauryl sodium sulfate;
(2) CNT is mixed with concentrated hydrochloric acid, be heated to 50 ℃ and stir 5h, then add ultrasonic processing 5h in chloroazotic acid,, dry in baking oven to neutral with distilled water flushing, add lauryl sodium sulfate to be uniformly dispersed;
(3) polyvinyl alcohol is dissolved in 90 ℃ of hot water, is made into concentration and is 15% the aqueous solution, stir 5h, add polyethylene glycol and scattered CNT, continue to stir 2h in 90 ℃ of water-baths, add nano silicon to stir 5h;
(4) mixed liquor is incubated 24h in 60 ℃ of water-baths, is poured on and uses the glass bar knifing on glass plate, immerse after air evaporation 30s in the saturated metabisulfite solution under room temperature, after 24h, taking-up gets final product with the distilled water washing.
Described polyvinyl alcohol average degree of polymerization is 1750 ± 50.
Described CNT is SWCN, and caliber is 0.5～1nm.
Described nano silicon particle diameter is 20～40nm.
CNT is novel One-dimensional nanoreticular carbon materials, since being found, has started the upsurge of people's researchs due to the performance of its unique structure and excellence.CNT is widely used in the fields such as hydrogen storage material, composite reinforcing agent, superconductor because having good mechanical property, electric property, toughness, the large characteristics such as specific area.The progress of nanometer technology makes the nano-porous films based on CNT be developed.
Nano silicon is one of ultra tiny New Inorganic Materials of extremely important high-tech, because of its particle diameter very little, specific area is large, adsorption power is strong, the surface can be large, and the aspects such as chemical purity is high, dispersive property good, thermal resistance, resistance have special performance, with its superior stability, reinforcement, thickening property and thixotropy, show unique characteristics in numerous subjects and field, the effect of not replacing is arranged.And because polyvinyl alcohol and nano silicon are all hydroaropic substances, polyvinyl alcohol has good wellability to the surface of nano silicon, and nano silicon has huge specific area and surface energy, has larger activity, polyvinyl alcohol can be adsorbed on nano-silica surface securely, make between polyvinyl alcohol and nano silicon and can form hydrogen bond, can improve the performance of polyvinyl alcohol milipore filter.
Advantage of the present invention: take polyvinyl alcohol as the film matrix material, add in casting solution a certain amount of with surfactant-dispersed good carbon nanotube functionalized with carboxylic acid group and nano silicon, take polyethylene glycol as pore-foaming agent, by immersion precipitation phase inversion masking.Prepared film had both kept the hydrophily of polyvinyl alcohol, thereby had stronger contamination resistance, and the intensity of the inorganic material of having withed a hook at the end and toughness have made up polyvinyl alcohol wet film intensity low, the not withstand voltage defective that gets.Prepared composite hyperfiltration membrane has stronger contamination resistance, high water flux and holds back preferably characteristic, but Reusability, long service life.
The specific embodiment
Embodiment one:
Prepare raw material by following weight proportion: 100 parts of polyvinyl alcohol; 2 parts of CNTs; 2 parts of nano silicons, 20 parts of polyethylene glycol; 30 parts of saturated metabisulfite solutions; 1 part of lauryl sodium sulfate.
Embodiment two:
Prepare raw material by following weight proportion: 100 parts of polyvinyl alcohol; 3 parts of CNTs; 1 part of nano silicon, 10 parts of polyethylene glycol; 35 parts of saturated metabisulfite solutions; 2 parts of lauryl sodium sulfate.
Embodiment three:
Prepare raw material by following weight proportion: 100 parts of polyvinyl alcohol; 1 part of CNT; 4 parts of nano silicons, 25 parts of polyethylene glycol; 40 parts of saturated metabisulfite solutions; 3 parts of lauryl sodium sulfate.
Embodiment four:
Prepare raw material by following weight proportion: 100 parts of polyvinyl alcohol; 6 parts of CNTs; 1 part of nano silicon, 25 parts of polyethylene glycol; 30 parts of saturated metabisulfite solutions; 3 parts of lauryl sodium sulfate.
Embodiment five:
Prepare raw material by following weight proportion: 100 parts of polyvinyl alcohol; 4 parts of CNTs; 2 parts of nano silicons, 22 parts of polyethylene glycol; 34 parts of saturated metabisulfite solutions; 4 parts of lauryl sodium sulfate.
Embodiment six:
Prepare raw material by following weight proportion: 100 parts of polyvinyl alcohol; 4 parts of CNTs; 2 parts of nano silicons, 20 parts of polyethylene glycol; 28 parts of saturated metabisulfite solutions; 4 parts of lauryl sodium sulfate.
The polyvinyl alcohol average degree of polymerization is 1750 ± 50.CNT is SWCN, and caliber is 0.5～1nm.The nano silicon particle diameter is 20～40nm.
CNT is mixed with concentrated hydrochloric acid, be heated to 50 ℃ and stir 5h, then add ultrasonic processing 5h in chloroazotic acid,, dry in baking oven to neutral with distilled water flushing, add lauryl sodium sulfate to be uniformly dispersed; Polyvinyl alcohol is dissolved in 90 ℃ of hot water, is made into concentration and is 15% the aqueous solution, stir 5h, add polyethylene glycol and scattered CNT, continue to stir 2h in 90 ℃ of water-baths, add nano silicon to stir 5h; Mixed liquor is incubated 24h in 60 ℃ of water-baths, be poured on and use the glass bar knifing on glass plate, immerse after air evaporation 30s in the saturated metabisulfite solution under room temperature, take out the CNT of the present invention, the nano silicon that get final product with the distilled water washing after 24h and be total to the modified polyvinylalcohol composite hyperfiltration membrane.
The performance test of composite hyperfiltration membrane:
(1) Mechanics Performance Testing: adopt electronic tensile machine to measure hot strength and the tension fracture elongation rate of composite hyperfiltration membrane, probe temperature is room temperature, and rate of extension is 2 mm/min.
(2) water flux experiment: at room temperature, film is placed in cup type ultrafilter, precompressed 1 h under 0.1MPa pressure collects the volume that sees through liquid in certain hour, the pure water flux of test compound film.
(3) film antifouling property test: be the stain resistance of investigating composite membrane, take distilled water and BSA solution as feed liquid, it tested.The pure water flux of composite membrane is J
0, composite membrane is surveyed its water flux after BSA pollutes be J
1, repeatedly rinses several times with distilled water after composite membrane pollutes, then to survey its water flux be J
2The computing formula of the resistance enhancement coefficient m of film and flux recovery rate Ф: m=(J
0-J
1)/J
1* 100%; Ф=J
2/ J
0* 100%.
(4) rejection test: at room temperature, the BSA standard liquid of a series of concentration of preparation is measured through ultraviolet-uisible spectrophotometer, obtains corresponding absorbance A, drawing standard curve A-CBSA.And then certain density BSA solution is filtered a period of time under certain pressure, after stability of flow, collect a certain amount of filtrate, measure respectively the A of material liquid and filtrate with ultraviolet-uisible spectrophotometer, can calculate corresponding concentration according to the calibration curve equation, then calculate the rejection R=(C of milipore filter
f-C
p)/C
f* 100%; C wherein
fThe concentration of material liquid, C
pSee through the concentration of liquid.
Test result sees Table 1
The performance test results of table 1 composite hyperfiltration membrane
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Hot strength/MPa | 8.75 | 9.56 | 10.32 | 8.79 | 9.78 | 10.12 |
| Elongation at break/% | 2.12 | 1.98 | 2.35 | 2.45 | 2.03 | 2.33 |
| Water flux/(Lm -2·h -1） | 129.6 | 132.6 | 142.3 | 126.4 | 134.2 | 121.8 |
| Resistance enhancement coefficient m | 0.32 | 0.29 | 0.33 | 0.28 | 0.30 | 0.31 |
| Flux recovery rate Ф | 88.32 | 80.56 | 85.73 | 86.12 | 89.34 | 87.67 |
| Rejection R | 0.81 | 0.79 | 0.77 | 0.85 | 0.86 | 0.84 |
Test result shows that composite hyperfiltration membrane has stronger contamination resistance, high water flux and holds back preferably characteristic.But and the composite hyperfiltration membrane Reusability, long service life.
In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of requirement of the present invention.
Claims (4)
1. a CNT, the nano silicon preparation method of modified polyvinylalcohol composite hyperfiltration membrane altogether is characterized in that comprising the following steps:
(1) prepare raw material by following weight proportion: 100 parts of polyvinyl alcohol; 1～6 part of CNT; 1～4 part of nano silicon, 10～25 parts of polyethylene glycol; 30～40 parts of saturated metabisulfite solutions; 1～6 part of lauryl sodium sulfate;
(2) CNT is mixed with concentrated hydrochloric acid, be heated to 50 ℃ and stir 5h, then add ultrasonic processing 5h in chloroazotic acid,, dry in baking oven to neutral with distilled water flushing, add lauryl sodium sulfate to be uniformly dispersed;
(3) polyvinyl alcohol is dissolved in 90 ℃ of hot water, is made into concentration and is 15% the aqueous solution, stir 5h, add polyethylene glycol and scattered CNT, continue to stir 2h in 90 ℃ of water-baths, add nano silicon to stir 5h;
(4) mixed liquor is incubated 24h in 60 ℃ of water-baths, is poured on and uses the glass bar knifing on glass plate, immerse after air evaporation 30s in the saturated metabisulfite solution under room temperature, after 24h, taking-up gets final product with the distilled water washing.
2. CNT according to claim 1, nano silicon are total to the preparation method of modified polyvinylalcohol composite hyperfiltration membrane, and it is characterized in that: described polyvinyl alcohol average degree of polymerization is 1750 ± 50.
3. CNT according to claim 1, nano silicon are total to the preparation method of modified polyvinylalcohol composite hyperfiltration membrane, and it is characterized in that: described CNT is SWCN, and caliber is 0.5～1nm.
4. CNT according to claim 1, nano silicon are total to the preparation method of modified polyvinylalcohol composite hyperfiltration membrane, and it is characterized in that: described nano silicon particle diameter is 20～40nm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113069933A (en) * | 2021-03-26 | 2021-07-06 | 东南大学 | Organic/inorganic composite membrane for separating N, N-dimethylformamide/water mixture and preparation method thereof |
| CN113172948A (en) * | 2021-04-29 | 2021-07-27 | 天津市伟星新型建材有限公司 | Anti-scaling floor heating pipeline with high thermal conductivity and preparation method thereof |
| CN113713629A (en) * | 2021-04-19 | 2021-11-30 | 保定源汉升新材料科技有限公司 | Efficient particulate matter adsorption material and preparation method and purification mode thereof |
| CN116808843A (en) * | 2023-08-30 | 2023-09-29 | 新乡学院 | Loaded MnO 2-X Carbon nano tube-polyvinyl chloride mixed matrix ultrafiltration membrane and preparation method thereof |
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| CN101039798A (en) * | 2004-10-06 | 2007-09-19 | 纽约州立大学研究基金会 | High flux and low fouling filtration media |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113069933A (en) * | 2021-03-26 | 2021-07-06 | 东南大学 | Organic/inorganic composite membrane for separating N, N-dimethylformamide/water mixture and preparation method thereof |
| CN113069933B (en) * | 2021-03-26 | 2022-10-14 | 东南大学 | Organic/inorganic composite membrane for separating N, N-dimethylformamide/water mixture and preparation method thereof |
| CN113713629A (en) * | 2021-04-19 | 2021-11-30 | 保定源汉升新材料科技有限公司 | Efficient particulate matter adsorption material and preparation method and purification mode thereof |
| CN113713629B (en) * | 2021-04-19 | 2024-06-11 | 保定源汉升新材料科技有限公司 | Efficient particulate matter adsorption material, preparation method and purification mode thereof |
| CN113172948A (en) * | 2021-04-29 | 2021-07-27 | 天津市伟星新型建材有限公司 | Anti-scaling floor heating pipeline with high thermal conductivity and preparation method thereof |
| CN116808843A (en) * | 2023-08-30 | 2023-09-29 | 新乡学院 | Loaded MnO 2-X Carbon nano tube-polyvinyl chloride mixed matrix ultrafiltration membrane and preparation method thereof |
| CN116808843B (en) * | 2023-08-30 | 2023-11-21 | 新乡学院 | Loaded MnO 2-X Carbon nano tube-polyvinyl chloride mixed matrix ultrafiltration membrane and preparation method thereof |
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Application publication date: 20130529 |