CN104474914B - A kind of nano-filtration membrane containing fibroin albumen and preparation method thereof - Google Patents
A kind of nano-filtration membrane containing fibroin albumen and preparation method thereof Download PDFInfo
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- CN104474914B CN104474914B CN201410741617.9A CN201410741617A CN104474914B CN 104474914 B CN104474914 B CN 104474914B CN 201410741617 A CN201410741617 A CN 201410741617A CN 104474914 B CN104474914 B CN 104474914B
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Abstract
The present invention relates to a kind of nano-filtration membrane containing fibroin albumen, the composite fibre being made up of fibroin albumen and nano-sized carbon is constituted, unit plane integrated membrane is contained within the fibroin albumen that weight ratio is 70 95%, the Nano carbon balls that weight ratio is 3 30%, the thickness of filter membrane is 0.05 5 μm, the specific surface area of fiber is big, adsorption is strong, and intensity is big, durable.The preparation method of the nano-filtration membrane, comprises the steps：（1）, silkworm silk is put in sodium carbonate liquor, boil degumming, be filtrated to get fibroin albumen coarse fodder；（2）, the fibroin albumen coarse fodder for obtaining is put in calcium chloride solution and is dissolved, obtain fibroin albumen just liquid；（3）, by the fibroin albumen for obtaining, just liquid carries out desalination, obtains silk protein liquid；（4）, in the silk protein liquid for obtaining add Nano carbon balls, ultrasound wave to be uniformly dispersed, obtain spinning liquid；（5）, resulting spinning liquid carried out into electrostatic spinning, obtain nano-filtration membrane.
Description
Technical field
The present invention relates to water filtration technology field, more particularly to a kind of nano-filtration membrane containing fibroin albumen and its system
Preparation Method.
Background technology
Silkworm silk is a kind of native protein with good characteristic, as long as being made up of sericin and fibroin, wherein fibroin is main
Composition is wanted, the 70-80% of silk protein weight is accounted for, it is for the use of fibroin albumen, ancient toward so far, always as silk, clothes
Decorations, in order to further improve the value of fibroin albumen, in recent years, be devoted to fibroin albumen other fields research gradually
Increase, one of which is research of the fibroin albumen in film field, such as the Chinese invention patent of Patent No. CN103341209 in
A kind of silk fibroin nano-fiber film and preparation method disclosed in 9 days October in 2013, with natural silk as primary raw material, Jing
Acidic salt solution dissolving, film forming, after desalination, then spinning liquid, Jing electrostatic spinning systems are configured to formic acid or hexafluoroisopropanol dissolving
For into fibroin albumen based nano-fiber film, membrane structure stablizes controllable, biocompatibility well, can be used as biomaterial for medical purpose.This
The preparation method of disclosure of the invention is simple, flow process is short, film forming and spinning efficiency are high, is suitable for industrialization large-scale production.But should
The film that method is obtained also has some shortcomings：1st, as the characteristic of silkworm silk causes to obtain that film strength is low, support performance is poor；2nd, can not
Meet the requirement of filter membrane.
The content of the invention
An object of the present invention is to provide a kind of nano-filtration membrane containing fibroin albumen；
The second object of the present invention is to provide the preparation method of the nano-filtration membrane containing fibroin albumen.
One of in order to achieve the above object, the technical solution used in the present invention is as follows, a kind of nanometer containing fibroin albumen
Filter membrane, the composite fibre being made up of fibroin albumen and nano-sized carbon are constituted, and unit plane integrated membrane is contained within weight ratio for 70-95%'s
Fibroin albumen, weight ratio Nano carbon balls or CNT for 3-30%, a diameter of 20-30nm of the composite fibre, filter membrane
Thickness be 0.05-5 μm, the specific surface area of fiber is big, and adsorption is strong, and intensity is big, durable.
Two in order to achieve the above object, the technical solution used in the present invention is as follows：A kind of nanometer containing fibroin albumen
The preparation method of filter membrane, comprises the steps：
（1）, silkworm silk is put into water or mass fraction for the sodium carbonate liquor of 6-10%, boil degumming 10-20min, filter
Obtain fibroin albumen coarse fodder；
（2）, by the fibroin albumen coarse fodder for obtaining with 1：6-10（W/V）Proportioning to put into the mass fraction that boils be 35-
In 55% calcium chloride solution, 3-5mim is dissolved, obtain fibroin albumen just liquid；
（3）, by the fibroin albumen for obtaining, just liquid carries out desalination, obtains the silk protein liquid that concentration is 55-65%；
（4）, in the silk protein liquid for obtaining add Nano carbon balls or CNT, ultrasound wave to be uniformly dispersed, spun
Silk liquid；
（5）, resulting spinning liquid carried out into electrostatic spinning, obtain nano-filtration membrane.
Main component of the technical scheme with fibroin albumen as film, the fastness of fiber are good, and not easily broken, film is more durable,
Nano-sized carbon is added with, in addition to the characteristic for having nano-sized carbon, moreover it is possible to increase the overall intensity of film, make up fibroin albumen intensity difference not
Foot.
Preferably, step（3）In desalination adopt hollow fiber ultrafiltration membrane desalination mode, hollow fiber ultrafiltration membrane desalination
Time is short, and batch is big, and desalting efficiency is high, and simultaneously the first liquid of fibroin albumen can be concentrated.
Preferably, a diameter of 5-10nm of the Nano carbon balls or CNT, beneficial to being uniformly dispersed, and do not affect
The final physical performance of film.
Preferably, step（2）The pH of middle calcium chloride solution is 7.0-7.3, in micro- neutral solution, fibroin albumen
Dissolubility it is optimal.
Preferably, during the electrostatic spinning, it is 20-22 ㎝ to receive distance；Syringe needle internal diameter is 0.1-0.5mm；It is molten
Flow velocity is 0.5-1.0mL/h, and electrospinning parameters directly determine the quality of gained fiber, including diameter, diameter it is equal
Evenness etc., suitable parameter cause fibre diameter little, and diameter is homogeneous, and the scope of change is little, the performance to stablizing filter membrane
Play an important role.
Preferably, the preparation method also includes step（5）Afterwards wash film and dry process：The nanometer that spinning is obtained
Filter membrane is impregnated in being put into ethanol solution, and then low temperature dries.By alcohol dipping, the compactness of film more preferably, is conducive to improving
The strainability of film, and be conducive to stablizing for film properties, improve the service life of film；Low temperature dries prevents fibroin albumen from meeting height
Warm deformation causes the deformation of film.
Preferably, the volumetric concentration of the ethanol solution is 65-70%.
Preferably, dip time is 10-15min.
Preferably, described dry temperature for 30-40 DEG C.
By implementing above-mentioned technical proposal, the invention has the advantages that：Preparation method of the present invention is simple, flow process is short, into
Film is high with spinning efficiency, low for equipment requirements, low production cost；Resulting filtration film-strength is big, fiber not easy fracture, resistance to
With specific surface area is big, good filtration effect, stable performance.
Specific embodiment
With reference to specific embodiment, the present invention is explained further.
Embodiment 1：
A kind of preparation method of the nano-filtration membrane containing fibroin albumen, comprises the steps：（1）, silkworm silk is put into into water
In, degumming 20min is boiled, fibroin albumen coarse fodder is filtrated to get；
（2）, by the fibroin albumen coarse fodder for obtaining with 1：8（W/V）Proportioning put into the mass fraction for boiling be 35%,
During pH is 7.1 calcium chloride solution, 3mim is dissolved, obtain fibroin albumen just liquid；
（3）, by the fibroin albumen for obtaining, just liquid carries out desalination using hollow fiber ultrafiltration membrane, obtains the silk that concentration is 65%
Fibroin liquid；
（4）, in the silk protein liquid for obtaining, add the Nano carbon balls of a diameter of 5nm, ultrasound wave to be uniformly dispersed, spun
Silk liquid；
（5）, resulting spinning liquid is carried out electrostatic spinning, it is 0.1mm, solution to receive distance for 20 ㎝, syringe needle internal diameter
Flow velocity is 1.0mL/h, voltage is 10v, obtains nano-filtration membrane.
According to the preparation method of the present embodiment, the nano-filtration membrane for obtaining, by being combined that fibroin albumen and nano-sized carbon are constituted
Fiber is constituted, and unit plane integrated membrane is contained within the fibroin albumen that weight ratio is 95%, the Nano carbon balls that weight ratio is 3% or carbon nanometer
Pipe, a diameter of 22-25nm of the composite fibre, the thickness of filter membrane is 5 μm.
By the condition for controlling electrostatic spinning, the aperture of adjusting film obtains the filter membrane of different pore size, it is adaptable to different holes
On the product that footpath size needs, the microfiltration, ultrafiltration such as in water process, the mask of different filter effects etc..
Embodiment 2：
A kind of preparation method of the nano-filtration membrane containing fibroin albumen, comprises the steps：（1）, silkworm silk is put into into water
Or in the sodium carbonate liquor that mass fraction is 6%, degumming 10min is boiled, it is filtrated to get fibroin albumen coarse fodder；
（2）, by the fibroin albumen coarse fodder for obtaining with 1：6（W/V）Proportioning put into the mass fraction for boiling be 55%,
During pH is 7.3 calcium chloride solution, 4mim is dissolved, obtain fibroin albumen just liquid；
（3）, by the fibroin albumen for obtaining, just liquid carries out desalination using hollow fiber ultrafiltration membrane, obtains the silk that concentration is 55%
Fibroin liquid；
（4）, in the silk protein liquid for obtaining add a diameter of 6nm Nano carbon balls, ultrasound wave to be uniformly dispersed, obtain spinning
Liquid；
（5）, resulting spinning liquid is carried out electrostatic spinning, it is 22 ㎝ to receive distance；Syringe needle internal diameter is 0.5mm；Solution
Flow velocity is 0.5mL/h, voltage is 15v, obtains nano-filtration membrane.
According to the preparation method of the present embodiment, the nano-filtration membrane for obtaining, by being combined that fibroin albumen and nano-sized carbon are constituted
Fiber is constituted, and unit plane integrated membrane is contained within the fibroin albumen that weight ratio is 90%, the Nano carbon balls that weight ratio is 5% or carbon nanometer
Pipe, remaining is moisture, a diameter of 25-30nm of the composite fibre, and the thickness of filter membrane is 3.5 μm.
Embodiment 3：
A kind of preparation method of the nano-filtration membrane containing fibroin albumen, comprises the steps：（1）, silkworm silk is put into into water
Or in the sodium carbonate liquor that mass fraction is 8%, degumming 15min is boiled, it is filtrated to get fibroin albumen coarse fodder；
（2）, by the fibroin albumen coarse fodder for obtaining with 1：10（W/V）Proportioning put into the mass fraction for boiling be 40%,
During pH is 7.0 calcium chloride solution, 5mim is dissolved, obtain fibroin albumen just liquid；
（3）, by the fibroin albumen for obtaining, just liquid carries out desalination using hollow fiber ultrafiltration membrane, obtains the silk that concentration is 60%
Fibroin liquid；
（4）, in the silk protein liquid for obtaining add a diameter of 10nm CNTs, ultrasound wave to be uniformly dispersed, spun
Silk liquid；
（5）, resulting spinning liquid is carried out electrostatic spinning, it is 21 ㎝ to receive distance；Syringe needle internal diameter is 0.3mm；Solution
Flow velocity is 0.6mL/h, voltage is 15v, obtains nano-filtration membrane.
（6）, wash film and dry：The nano-filtration membrane that spinning is obtained is put in ethanol solution and is impregnated, then low temperature dries,
The volumetric concentration of ethanol solution is 65-70%, and the present embodiment is preferably 70%, and dip time is 10-15min, and the present embodiment is
Preferably 10mim, dries temperature for 30-40 DEG C, and the present embodiment is preferably 35 DEG C.
According to the preparation method of the present embodiment, the nano-filtration membrane for obtaining, by being combined that fibroin albumen and nano-sized carbon are constituted
Fiber is constituted, and unit plane integrated membrane is contained within the fibroin albumen that weight ratio is 70%, the Nano carbon balls that weight ratio is 26% or carbon nanometer
Pipe, remaining is water, a diameter of 20-25nm of the composite fibre, and the thickness of filter membrane is 0.05 μm.
Claims (8)
1. a kind of preparation method of the nano-filtration membrane containing fibroin albumen, it is characterised in that comprise the steps：
（1）, silkworm silk is put into water or mass fraction for the sodium carbonate liquor of 6-10%, boil degumming 10-20min, be filtrated to get
Fibroin albumen coarse fodder；
（2）, by the fibroin albumen coarse fodder for obtaining with 1：6-10（W/V）Proportioning put into the mass fraction that boils for 35-55%'s
In calcium chloride solution, 3-5mim is dissolved, obtain fibroin albumen just liquid；
（3）, by the fibroin albumen for obtaining, just liquid carries out desalination, obtains the silk protein liquid that concentration is 55-65%；
（4）, in the silk protein liquid for obtaining add Nano carbon balls or CNT, ultrasound wave to be uniformly dispersed, obtain spinning liquid；
（5）, resulting spinning liquid carried out into electrostatic spinning, obtain nano-filtration membrane；Unit area nano-filtration membrane is contained within
Weight ratio is the fibroin albumen of 70-95%, weight ratio for 3-30% Nano carbon balls or CNT, the thickness of nano-filtration membrane is
0.05-5μm。
2. a kind of preparation method of the nano-filtration membrane containing fibroin albumen according to claim 1, it is characterised in that step
（3）In desalination adopt hollow fiber ultrafiltration membrane desalination mode.
3. a kind of preparation method of the nano-filtration membrane containing fibroin albumen according to claim 1, it is characterised in that described
A diameter of 5-10nm of Nano carbon balls or CNT.
4. a kind of preparation method of the nano-filtration membrane containing fibroin albumen according to claim 1, it is characterised in that described
During electrostatic spinning, it is 20-22 ㎝ to receive distance；Syringe needle internal diameter is 0.1-0.5mm；Solution flow rate is 0.5-1.0mL/h.
5. a kind of preparation method of the nano-filtration membrane containing fibroin albumen according to claim 1, it is characterised in that also wrap
Include step（5）Afterwards wash film and dry process：The nano-filtration membrane that spinning is obtained is put in ethanol solution and is impregnated, it is then low
Temperature is dried.
6. a kind of preparation method of the nano-filtration membrane containing fibroin albumen according to claim 5, it is characterised in that described
The volumetric concentration of ethanol solution is 65-70%.
7. a kind of preparation method of the nano-filtration membrane containing fibroin albumen according to claim 6, it is characterised in that dipping
Time is 10-15min.
8. a kind of preparation method of the nano-filtration membrane containing fibroin albumen according to claim 5, it is characterised in that described
Temperature is dried for 30-40 DEG C.
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| CN105113038B (en) * | 2015-06-24 | 2017-05-31 | 南通纺织丝绸产业技术研究院 | A kind of loudspeaker diaphragm materials and preparation method thereof |
| CN108379933B (en) * | 2018-02-10 | 2021-01-15 | 北京清科丝宇技术有限公司 | Silk fibroin nanofiber filtering material and air filtering equipment based on filtering material |
| CN108998845B (en) * | 2018-06-28 | 2021-04-09 | 东莞市春藤实业有限公司 | High-water-absorption and high-air-permeability biomass fiber and preparation method thereof |
| CN109853068B (en) * | 2019-01-30 | 2021-08-10 | 东华大学 | Carbon quantum dot/fibroin composite nanofiber and preparation method and application thereof |
| CN111350029A (en) * | 2020-02-02 | 2020-06-30 | 江苏大学 | Fibroin-based multifunctional nanofiber membrane for smoke filtration and preparation method thereof |
| CN111748906A (en) * | 2020-07-06 | 2020-10-09 | 浙江理工大学 | Waste silk-based flexible carbon nanofiber membrane and preparation method thereof |
| CN112326743B (en) * | 2020-11-05 | 2024-01-16 | 重庆医科大学 | C-SF-FA flexible conductive film based on silk fibroin, wearable wound monitoring sensor and preparation method thereof |
| CN112707538B (en) * | 2020-12-08 | 2023-04-21 | 湖北百清环保技术有限公司 | Advanced membrane oxidation treatment cultivation wastewater technology |
| CN115341339B (en) * | 2022-08-25 | 2024-03-22 | 武汉大学 | Silk fibroin composite fiber film and method for detecting and analyzing perfluoro-type compounds |
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| CN1831219A (en) * | 2005-03-10 | 2006-09-13 | 北京化工大学 | Hybridized fiber contg. high molecular material, carbon material and hydroxy apatite and its prepn. method |
| CN101077473A (en) * | 2007-06-22 | 2007-11-28 | 上海兰度科技有限公司 | Novel environmental protection fiber film material and its preparation method |
| CN103657256A (en) * | 2012-09-24 | 2014-03-26 | 步世忠 | Nasal cavity filter membrane for filtering PM (Particulate Matter) 2.5 particles |
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