CN107812453A - A kind of preparation method of the biodegradable water-oil separationg film of multifunctional application - Google Patents
A kind of preparation method of the biodegradable water-oil separationg film of multifunctional application Download PDFInfo
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- CN107812453A CN107812453A CN201711044869.6A CN201711044869A CN107812453A CN 107812453 A CN107812453 A CN 107812453A CN 201711044869 A CN201711044869 A CN 201711044869A CN 107812453 A CN107812453 A CN 107812453A
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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
- B01D71/08—Polysaccharides
- B01D71/10—Cellulose; Modified cellulose
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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
- B01D67/0002—Organic membrane manufacture
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/26—Further operations combined with membrane separation processes
- B01D2311/2696—Catalytic reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/39—Electrospinning
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
Abstract
The invention discloses a kind of preparation method of the biodegradable water-oil separationg film of multifunctional application, including（1）Prepared polymer Matrix Solution,（2）Electrospun nanofibers film,（3）By the step of hydro-thermal method one realize layering micro nano structure construct and the N doping of titanium dioxide, obtain biodegradable water-oil separationg film.Film prepared by the present invention under visible light exposure just can effectively degradating organic dye and can high efficiency oil-water separation, realize " material is dual-purpose ", on the one hand because it just can degradating organic dye under visible light exposure, not only green, environmental protection, energy consumption are low, secondary pollution problem caused by it also avoid sorbing material De contamination, on the other hand due to the biodegradable of itself, environment will not be damaged, solve the problems, such as the postpositive disposal of not Biodegradable material, had great application prospect in dye wastewater, oily waste water treatment and oil recycling etc..
Description
Technical field
The invention belongs to chemical industry and polymer-function material technical field, and in particular to a kind of multifunctional application can biology
The preparation method for water-oil separationg film of degrading.
Background technology
Water is to maintaining the life of the mankind and the sustainable development of society to play vital effect.Along with the fast of population
Speed increase and industrialized high speed development, water pollution turn into one it is very severe the problem of.In a variety of water pollutant sources, nothing
Machine（Oil and aromatic compound）With it is organic（Dyestuff）It is major pollutants.On the one hand, petrochemical industry, machine-building, communications and transportation,
Leather processing, weaving manufacture, food processing, medicine the water for kitchen use in industrial process, daily life such as produce and happened occasionally
Crude Oil at Sea leakage accident be all inevitably generated a large amount of oily waste waters, pollute water environment for the survival of mankind.No matter
It is the recycling from petroleum resources, or the angle from purification sewage environmental protection, require and oil-polluted water is carried out effectively
Separation.The separation of oil and water realizes that sustainable development is significant to the mankind.It has been reported that polyvinylidene fluoride film etc. it is super
Oleophylic super-hydrophobic material has higher oil-water separation, but because its lipophile make it that oil was oozing in separation process
Oily pollution is caused in membrane material or even is blocked so as to influence the service life of film and number, and this lipophilic-hydrophobic property material exists
Extras are needed to produce power, separation costs and high energy consumption in separation process.In recent years, opened by fish scale and clam shell
Hair, the underwater superoleophobic property material prepared by bionics principle is extensively concerned, and this material can not only avoid water-treated
It is polluted by the oil in journey, and only can realizes that oil is separated from water by gravity, separation process is simple, energy consumption is low.Copper mesh, stainless (steel) wire,
The underwater superoleophobic property water-oil separating material such as titanium net, glass fiber filter, polyvinylidene fluoride film, PS membrane is all successful case
Example.However, these materials are not biodegradable, its is rearmounted be treated as one it is huge the problem of, such as directly abandon and burning, no
Secondary pollution can be caused with can avoiding.
On the other hand, as the growth of population, the demand of dyestuff increase.And the preparation of dyestuff and use process will produce greatly
The waste water from dyestuff of amount.Organic dyestuff it is complicated and not biodegradable, its intractability is big, and ecological environment and the mankind are good for
Health forms grave danger.In recent years, organic dyestuff sorbing material such as aeroge, microballoon, hydrogel etc. is by wide coverage, but this
Dyestuff in water has simply been transferred in sorbing material by a little materials, does not remove dyestuff thoroughly, and its De contamination is handled
Need to use a large amount of solvents, be inevitably generated secondary pollution.Realize that degradation of organic dyes has very big prospect.Titanium dioxide
（TiO2）Due to its chemically stable, abundance, nontoxic, cost is low, is a kind of wide variety of photochemical catalyst, under ultraviolet light
Can effective degradating organic dye（Methylene blue）.But uviol lamp expensive equipment, energy resource consumption is larger, in addition ultraviolet light irradiation
People is known from experience and caused damage.By doping, TiO can be made2Band gap narrow so as to improve photocatalysis efficiency, and can be under visible light
Degradating organic dye, cost is low, Non-energy-consumption, green and healthy, and can thoroughly remove organic dyestuff, will not bring secondary pollution.Its
In, N doping cost is relatively low and photocatalysis efficiency is high, favorable repeatability.
Cellulose is a kind of polymer synthesized by plant by photosynthesis, is that yield highest is naturally high in nature
Molecular material, it is considered to be it is a kind of inexhaustible, with its renewable resource not to the utmost.Cellulose has renewable, biological drop
The advantages that solving, be environment-friendly, pollution-free, it is the main source of the sustainable material of technical grade.But also electrostatic is not used so far
Spinning fibre element film be matrix prepare can water-oil separating and can degradating organic dye multifunctional application biodegradable oil
The report of water seperation film.
The content of the invention
In order to solve the deficiencies in the prior art, it is an object of the invention to provide a kind of easy, efficient, environmental protection multi-functional
The preparation method of the biodegradable water-oil separationg film of application, realize " material uses ", water-oil separating and can be realized can
See degradating organic dye under light, be expected to promote the development of multi-functional material for water treatment, new direction provided for material for water treatment, no
Only solves the water pollution problems of current serious（Oil and organic dyestuff are the major pollutants of water pollution）, also solve water-oil separating
The postpositive disposal problem of material and the secondary pollution problem of organic dyestuff sorbing material.
In order to realize above-mentioned technical purpose, the present invention uses following technical scheme：
A kind of preparation method of the biodegradable water-oil separationg film of multifunctional application, comprises the following steps：
（1）Prepared polymer Matrix Solution
Polymeric matrix is activated first, the present invention is activated using the method for exchange of solvent, and high-temperature activation can cause fiber
Degraded, and the method for exchange of solvent hardly causes the degraded of cellulose, the activation is to soak polymeric matrix successively
The 1-2 hours in water, methanol, dimethyl acetamide, polymeric matrix need to enter polymeric matrix after soaking in a kind of solvent
Row, which filters, removes the solvent, then polymeric matrix is dipped into another solvent again, the effect of exchange of solvent is weak
The strong interaction of hydrogen bond of cellulose interchain obtains loose conformation, and polymeric matrix finally is dissolved in into dicyandiamide solution
In, obtain 1 ~ 2 wt% polymer matrix liquid solutions；
When the polymeric matrix is cellulose, lignin, hemicellulose, chitosan, chitin, the dicyandiamide solution is
DMAc/LiCl solution, the ratio of the DMAc and LiCl are 92-93g: 7-8g；
When the polymeric matrix is polyvinyl alcohol, the dicyandiamide solution is the isopropanol/water solution that volume ratio is 7/3；
When the polymeric matrix is cellulose acetate, the dicyandiamide solution is acetic acid/acetone soln that volume ratio is 1/1；
（2）Electrospun nanofibers film
Using running water as coagulating bath, above-mentioned polymer matrix liquid solution is fitted into syringe, is loaded on No. 21 syringe needles, then
The spinning under 0.3 ~ 0.45 mL/min fltting speed, positive and negative voltage are respectively set as 20 ~ 23 KV and -1 ~ -0.9 KV, covered
Silk is crimped film forming by the metal roller for having aluminium foil as collection device, roller, produces the nano fibrous membrane；
（3）Prepare the biodegradable water-oil separationg film of multifunctional application
After above-mentioned nano fibrous membrane freeze-drying, it is immersed in the nitrogenous mixed solution of TiO 2 precursor, at 80-200 DEG C
Lower hydro-thermal reaction 1-30 h, hydro-thermal reaction use deionized water rinsing after terminating, are freeze-dried 12h afterwards, produce multifunctional application
Biodegradable water-oil separationg film.
The step（3）, the TiO 2 precursor used in hydro-thermal reaction is the fourth fat of metatitanic acid four, isopropyl titanate,
One kind in titanium tetrachloride or titanium potassium oxalate.
The step（3）, the nitrogen-containing material that uses in hydro-thermal reaction is ammoniacal liquor, melamine, urea, ammonium chloride, hydrazine, salt
One kind in sour guanidine or triethylamine.
The step（3）, the solvent of hydro-thermal reaction is in aqueous hydrochloric acid solution, aqueous hydrogen peroxide solution or glycerol-alcohol solution
One kind.
Step（3）Carried titanium dioxide and titanium dioxide on electrospun fibers element film are realized by the step of hydro-thermal method one
N doping.On the one hand by regulating and controlling the dosage of TiO 2 precursor, hydrothermal temperature, reaction time, control is carried on
The form of the titanium dioxide granule on electrospun fibers element film surface, constructs layering micro nano structure, it is super hydrophilic to impart material
Underwater superoleophobic property, so as to for water-oil separating.On the other hand, nitrogen source species and dosage are screened and regulated and controled, obtained
Just there is the nitrogen-doped titanium dioxide of preferable photocatalysis efficiency under visible light illumination, available for degradation of organic dyes, realize
With regard to energy degradating organic dye and the dual effect of water-oil separating under visible light exposure.
Compared to super oleophylic super-hydrophobic material, underwater superoleophobic property material have service life is long, antifouling property is good, point
From low power consumption and other advantages, there is huge commercial application potentiality.But underwater superoleophobic property material is non-renewable at present and can not
Biodegradation, easily to environmental concerns.In addition, most of organic dyestuff sorbing materials with organic dyestuff due to simply being combined
Not by degradation of organic dyes, although eliminating the organic dyestuff in water, it has been retained in sorbing material, has inevitably made
Into secondary pollution.The present invention uses above technical scheme, first by polymer wiring solution-forming spinning film forming, passes through presoma, nitrogen source
Species and dosage, reaction time, reaction temperature regulation and control titanium dioxide pattern and raising photocatalysis efficiency.Pass through a step hydro-thermal
Method prepares the biodegradable water-oil separationg film of multifunctional application, it is not necessary to additional post-processing step, it is real in water-heat process
Existing micro nano structure construct and the N doping of titanium dioxide, preparation process is simple, efficiently, easily promotes.In addition, the material exists
Just effectively degradation of dye and water-oil separating can be realized under visible light exposure, green, environmental protection, energy consumption be low, without environment hidden danger.Due to
Material itself is biodegradable, effectively solves the problems, such as the postpositive disposal of current water-oil separating material, will not produce secondary dirt
Dye.
The present invention compared with prior art, has the advantages that：
1st, the present invention uses cellulose as matrix material, and cellulose has that wide material sources, cost are low, renewable, biodegradable,
The features such as environment-friendly.
2nd, the range of choice of Inventive polymers matrix is very wide, can be selected cellulose, lignin, hemicellulose, chitosan,
The biological materials such as chitin are that the synthetic materials such as cellulose acetate, polyvinyl alcohol also can be selected as matrix in matrix material
Material carries out electrostatic spinning, can prepare multi-functional water-oil separationg film.Different polymer are used to be obtained for matrix material
Hierarchy film has different physics, chemical property, can be applicable to different field.
3rd, the polymeric matrix that the present invention selects is mostly natural polymer, has renewable, biodegradable, environment friend
The features such as good.Matrix is done due to stainless (steel) wire is not used, avoids and loses lacking for oil-water separation because strong acid and strong base corrodes
Point, remains to holding high separating efficiency under high salt concentration, strong acid, basic conditions, and use range is wider.
4th, the present invention can be achieved with load and the titanium dioxide N doping of titanium dioxide by one-step method, assign material oil
Water separates and two kinds of functions of degradating organic dye under visible ray.The process is simple, without using toxic reagent, without toxic and harmful gas
Material produces.
5th, water-oil separationg film produced by the present invention has the advantages of high porosity, specific area, therefore film is with higher
Water flux, disengaging time are short.
6th, water-oil separationg film strong alkali-acid resistance high salt produced by the present invention, available for the profit point under acid, alkalescence condition
From and Crude oil from CNOOC leakage improvement.
7th, water-oil separationg film produced by the present invention just effectively degradating organic dye and can realize oil-containing under visible light exposure
Sewage efficiently separates, can " material uses ", while complete the processing of oil-polluted water and waste water from dyestuff.
8th, film prepared by the present invention has very excellent water-oil separating performance, by the dosage, the reaction that change presoma
Time, reaction temperature, the hierarchy film with different-shape can be prepared.
9th, the present invention regulates and controls photocatalysis efficiency by changing nitrogen source species and dosage, can prepare under visible light exposure
Just there is the multi-functional water-oil separationg film of excellent degradation of organic dyes performance, overcome secondary existing for sorbing material De contamination
Pollution problem.
10th, water-oil separationg film produced by the present invention is biodegradable, will not produce secondary pollution, overcomes and biological can not drop
Solve the postpositive disposal problem of water-oil separating material.
11st, the biodegradable water-oil separationg film of multifunctional application is in atmosphere to the contact angle of water close to 0 °, in water
150 ° are more than to the contact angle of oil, there is super hydrophilic underwater superoleophobic property, efficiently separating for oil-polluted water is can be achieved with by gravity.
12nd, by changing the rotating speed of collecting drum, the degree of orientation of fiber can be regulated and controled.
13rd, by changing the intensity of spin rate, the distance of spinning nozzle to collecting drum and voltage, fiber can be regulated and controled
Diameter.
Brief description of the drawings
The present invention is further elaborated with reference to the accompanying drawings and detailed description.
Fig. 1 is the SEM figures of the water-oil separationg film prepared by embodiment 1.
The photo that solution not different Fig. 2 is dripped in the water-oil separationg film of embodiment 1；
Wherein,（a）For 4 μ L water droplets to the photo in water-oil separationg film；（b）Dripped to for the dichloroethanes of 2 μ L 1,2 under water
Photo on water-oil separationg film film.
Fig. 3 is n-hexane/aqueous emulsion using the pictorial diagram and corresponding before and after the water-oil separating UF membrane of embodiment 1
Light scattering photo.
Fig. 4 is the methylene blue solution ultra-violet absorption spectrum before and after being irradiated 1 hour under 1000w selenium lamps.
Embodiment
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.
Embodiment 1
Preparation method using cellulose as the biodegradable water-oil separationg film of the multifunctional application of matrix
（1）Prepare cellulose solution
The cellulose fibres such as cotton, wood pulp, bamboo pulp are activated first, i.e., soaked the cellulose fibres such as cotton, wood pulp, bamboo pulp successively
1 hour in water, methanol, dimethyl acetamide (DMAc), immersion every time is left bubble along with filtering with removing in cellulose
Solvent is soaked, is finally 92 in DMAc/LiCl ratios by the cellulose dissolution after activation:In 8 dicyandiamide solution, 1.5wt% is obtained
Cellulose solution.
（2）Electrostatic spinning prepares cellulose nano-fibrous membrane
Using running water as coagulating bath, the cellulose solution prepared is fitted into syringe, then 0.35 mL/min's
Spinning under fltting speed, generating positive and negative voltage are respectively set as 21 KV and -1KV, and the metal roller overlying aluminium foil of rotation fills as collection
Put, silk is crimped film forming by roller, removes solvent, and cellulose nano-fibrous membrane is made.
（3）Hydro-thermal method prepares the biodegradable water-oil separationg film of multifunctional application
After cellulose nano-fibrous membrane freeze-drying, it is put into equipped with mixed solution（Fourth fat=30/30/ of ammoniacal liquor/hydrochloric acid/metatitanic acid four
1.5）Reactor in, at 150 DEG C after hydro-thermal reaction 4h, take out freeze-drying 12h, produce the biodegradable of multifunctional application
Water-oil separationg film.
Pass through Fig. 1（SEM）As can be seen that titanium dichloride load is on cellulose nano-fibrous, and form substantial amounts of point
Layer petal-like structures.By Fig. 2（a）It can be seen that when water drop contact is to film, water droplet infiltrates quickly, and water contact angle connects film in atmosphere
Nearly 0 °, show Superhydrophilic；By Fig. 2（b）It can be seen that it is in spherical that 1,2 dichloroethanes, which is rested on film, underwater oily contact angle is more than
150 °, underwater superoleophobic property is shown, therefore the material has super hydrophilic underwater superoleophobic property, has opposite infiltration to oil and water
Property, so as to the potentiality for efficiently separating oil-polluted water.From the figure 3, it may be seen that the water-oil separationg film of the present invention can be by oil red O stain
The isolated almost colourless transparent filtrate of n-hexane/aqueous emulsion, light scattering photo further prove the filtrate after separation almost
Exist without oil droplet, illustrate its high separating efficiency, pass through total organic carbon analyzer（TOC）Separative efficiency is measured more than 99%.Separately
Outside, water-oil separationg film of the invention has also carried out the degradation of organic dyes experiment under visible light exposure, passes through uv-spectrophotometric
Measure, after visible light exposure 1h, more than 80% is reached to the degradation efficiency of methylene blue, sees Fig. 4.In summary, it is of the invention
Water-oil separationg film effective degraded of methylene blue and efficiently separating for oil-polluted water are achieved that under visible light exposure.
There is the reason for multifunctional application under water-oil separationg film visible light exposure prepared by the present invention：By hydro-thermal method in fibre
Plain nano fibrous membrane area load titanium dioxide is tieed up, carrying out regulation and control to reaction condition has constructed layering micro nano structure.Due to material
The high surface energy of material and be layered the collective effect of micro nano structure and with super hydrophilic underwater superoleophobic property, opposite wetability
So that material can carry out effective water-oil separating.In addition, changing the band gap of titanium dioxide after titanium dioxide N doping, improve
Photocatalysis efficiency, with regard to great amount of hydroxy group free radical can be produced under visible light exposure, so as to which the effective drop of organic dyestuff can be realized
Solution.
Embodiment 2
Preparation method using lignin as the biodegradable water-oil separationg film of the multifunctional application of matrix
（1）Prepare lignin liquor
Lignin is activated first, lignin is immersed in in water, methanol, dimethyl acetamide (DMAc) 1.5 hours successively, often
Secondary immersion is along with filtering to remove the immersion solvent in lignin, finally by the lignin dissolution activated in DMAc/LiCl
Ratio is 93:In 7 dicyandiamide solution, 1 wt% lignin liquor is obtained.
（2）Electrostatic spinning prepares lignin nano fibrous membrane
Using running water as coagulating bath, the lignin liquor prepared is fitted into syringe, then pushing away in 0.35 mL/min
Enter spinning under speed, generating positive and negative voltage is respectively set as 21 KV and -1KV, and the metal roller overlying aluminium foil of rotation fills as collection
Put, silk is crimped film forming by roller, removes solvent, and lignin nano fibrous membrane is made.
（3）Hydro-thermal method prepares the biodegradable water-oil separationg film of multifunctional application
After the freeze-drying of lignin nano fibrous membrane, it is put into equipped with mixed solution（The melamine aqueous solution/hydrochloric acid/metatitanic acid four
Fourth fat=30/30/1.2）Reactor in, at 150 DEG C after hydro-thermal reaction 4h, take out freeze-drying 12h, produce multifunctional application
Biodegradable water-oil separationg film.
Embodiment 3
Preparation method using chitin as the biodegradable water-oil separationg film of the application of matrix
（1）Prepare chitin solution
Chitin is activated first, chitin is immersed in in water, methanol, dimethyl acetamide (DMAc) 1.5 hours successively, often
The chitin activated, to remove the immersion solvent in chitin, is finally dissolved in DMAc/LiCl by secondary immersion along with filtering
Ratio is 92:In 8 dicyandiamide solution, 2wt% chitin solution is obtained.（2）Electrostatic spinning prepares chitin nano fiber film
Using running water as coagulating bath, the chitin solution prepared is fitted into syringe, then pushing away in 0.3 mL/min
Enter spinning under speed, generating positive and negative voltage is respectively set as 20 KV and -1KV, and the metal roller overlying aluminium foil of rotation fills as collection
Put, silk is crimped film forming by roller, removes solvent, and chitin nano fiber film is made.
（3）Hydro-thermal method prepares the biodegradable water-oil separationg film of multifunctional application
After the freeze-drying of chitin nano fiber film, it is put into equipped with mixed solution（Ammoniacal liquor/hydrochloric acid/metatitanic acid isopropyl ester=30/30/
1.5）Reactor in, at 150 DEG C after hydro-thermal reaction 4h, take out freeze-drying 12h, produce the biodegradable of multifunctional application
Water-oil separationg film.
Embodiment 4
Preparation method using chitosan as the biodegradable water-oil separationg film of the multifunctional application of matrix
（1）Prepare chitosan solution
Chitosan is activated first, chitosan is immersed in in water, methanol, dimethyl acetamide (DMAc) 1 hour successively, every time
The chitosan activated, to remove the immersion solvent in chitosan, is finally dissolved in DMAc/LiCl ratios by immersion along with filtering
Example is 92:In 8 dicyandiamide solution, 2wt% chitosan solution is obtained.
（2）Electrostatic spinning prepares chitosan nano fiber membrane
Using running water as coagulating bath, the chitosan solution prepared is fitted into syringe, then pushing away in 0.45 mL/min
Enter spinning under speed, generating positive and negative voltage is respectively set as 23 KV and -1KV, and the metal roller overlying aluminium foil of rotation fills as collection
Put, silk is crimped film forming by roller, removes solvent, and chitosan nano fiber membrane is made.
（3）Hydro-thermal method prepares the biodegradable water-oil separationg film of multifunctional application
After chitosan nano fiber membrane freeze-drying, it is put into equipped with mixed solution（The fourth fat of ammoniacal liquor/glycerol-alcohol/metatitanic acid four=
10/50/2.5）Reactor in, at 150 DEG C after hydro-thermal reaction 6h, take out freeze-drying 12h, produce giving birth to for multifunctional application
Thing degraded water-oil separationg film.
Embodiment 5
Preparation method using polyvinyl alcohol as the biodegradable water-oil separationg film of the application of matrix
（1）Prepare poly-vinyl alcohol solution
Dissolve polyvinyl alcohol in isopropanol/water（7/3,v/v）In dicyandiamide solution, 1.5wt% poly-vinyl alcohol solution is obtained.
（2）Electrostatic spinning prepares polyvinyl alcohol nanofiber membrane
Using running water as coagulating bath, the poly-vinyl alcohol solution prepared is fitted into syringe, then 0.35 mL/min's
Spinning under fltting speed, generating positive and negative voltage are respectively set as 23 KV and -0.5KV, and the metal roller overlying aluminium foil of rotation is as collection
Silk is crimped film forming by device, roller, removes solvent, and polyvinyl alcohol nanofiber membrane is made.
（3）Hydro-thermal method prepares the biodegradable water-oil separationg film of multifunctional application
After polyvinyl alcohol nanofiber membrane freeze-drying, it is put into and mixed solution is housed（Aqueous solution of urea/hydrochloric acid/metatitanic acid
Four fourth fat=30/30/1.8）Reactor in, at 180 DEG C after hydro-thermal reaction 4h, take out freeze-drying 12h, produce it is multi-functional should
Biodegradable water-oil separationg film.
Embodiment 6
Preparation method using cellulose acetate as the biodegradable water-oil separationg film of the application of matrix
（1）Prepare cellulose acetate solution
Cellulose acetate is dissolved in acetic acid/acetone（1/1,v/v）In dicyandiamide solution, 2wt% cellulose acetate solution is obtained.
（2）Electrostatic spinning prepares cellulose acetate nano fibrous membrane
Using running water as coagulating bath, the cellulose acetate solution prepared is fitted into syringe, then in 0.35 mL/min
Fltting speed under spinning, generating positive and negative voltage is respectively set as 21KV and -0.9KV, and the metal roller overlying aluminium foil of rotation is as receiving
Silk is crimped film forming by acquisition means, roller, removes solvent, and cellulose acetate nano fibrous membrane is made.
（3）Hydro-thermal method prepares the biodegradable water seperation film of multifunctional application
After the freeze-drying of cellulose acetate nano fibrous membrane, it is put into equipped with mixed solution（Triethylamine aqueous solution/hydrochloric acid/metatitanic acid
Four fourth fat=30/30/1.5）Reactor in, at 160 DEG C after hydro-thermal reaction 4h, take out freeze-drying 12h, produce it is multi-functional should
Biodegradable water-oil separationg film.
Embodiment 7
Preparation method using cellulose as the biodegradable water-oil separationg film of the multifunctional application of matrix
（1）Prepare cellulose solution（With embodiment 1）
（2）Electrostatic spinning prepares cellulose nano-fibrous membrane（With embodiment 1）
（3）Hydro-thermal method prepares the biodegradable water-oil separationg film of multifunctional application
After cellulose nano-fibrous membrane freeze-drying, it is put into equipped with mixed solution（Ammonium chloride/hydrogen peroxide/titanium tetrachloride=
30/30/1.0）Reactor in, at 80 DEG C after hydro-thermal reaction 30h, take out freeze-drying 11h, produce giving birth to for multifunctional application
Thing degraded water-oil separationg film.
Embodiment 8
Preparation method using cellulose as the biodegradable water-oil separationg film of the multifunctional application of matrix
（1）Prepare cellulose solution（With embodiment 1）
（2）Electrostatic spinning prepares cellulose nano-fibrous membrane（With embodiment 1）
（3）Hydro-thermal method prepares the biodegradable water-oil separationg film of multifunctional application
After cellulose nano-fibrous membrane freeze-drying, it is put into equipped with mixed solution（Hydrazine/glycerol-alcohol/titanium potassium oxalate=30/30/
1.5）Reactor in, at 200 DEG C after hydro-thermal reaction 10h, take out freeze-drying 13h, produce multifunctional application can biology drop
Solve water-oil separationg film.
Embodiment 9
Preparation method using cellulose as the biodegradable water-oil separationg film of the multifunctional application of matrix
（1）Prepare cellulose solution（With embodiment 1）
（2）Electrostatic spinning prepares cellulose nano-fibrous membrane（With embodiment 1）
（3）Hydro-thermal method prepares the biodegradable water-oil separationg film of multifunctional application
After cellulose nano-fibrous membrane freeze-drying, it is put into equipped with mixed solution（The fourth fat of guanidine hydrochloride/hydrogen peroxide/metatitanic acid four=
30/30/1.2）Reactor in, at 100 DEG C after hydro-thermal reaction 150h, take out freeze-drying 12h, produce multifunctional application can
Biodegradable water-oil separationg film.
Claims (4)
- A kind of 1. preparation method of the biodegradable water-oil separationg film of multifunctional application, it is characterised in that：It includes following step Suddenly：（1）Prepared polymer Matrix SolutionPolymeric matrix is activated first, i.e., it is small that polymeric matrix is immersed in 1-2 in water, methanol, dimethyl acetamide successively When, finally polymeric matrix is dissolved in dicyandiamide solution, obtains 1 ~ 2 wt% polymer matrix liquid solution；When the polymeric matrix is cellulose, lignin, hemicellulose, chitosan, chitin, the dicyandiamide solution is DMAc/LiCl solution, the ratio of the DMAc and LiCl are 92-93g: 7-8g；When the polymeric matrix is polyvinyl alcohol, the dicyandiamide solution is the isopropanol/water solution that volume ratio is 7/3；When the polymeric matrix is cellulose acetate, the dicyandiamide solution is acetic acid/acetone soln that volume ratio is 1/1；（2）Electrospun nanofibers filmUsing running water as coagulating bath, above-mentioned polymer matrix liquid solution is fitted into syringe, is loaded on No. 21 syringe needles, then The spinning under 0.3 ~ 0.45 mL/min fltting speed, positive and negative voltage are respectively set as 20 ~ 23 KV and -1 ~ -0.9 KV, covered Silk is crimped film forming by the metal roller for having aluminium foil as collection device, roller, produces the nano fibrous membrane；（3）Prepare the biodegradable water-oil separationg film of multifunctional applicationAfter above-mentioned nano fibrous membrane freeze-drying, it is immersed in the nitrogenous mixed solution of TiO 2 precursor, at 80-200 DEG C Lower hydro-thermal reaction 1-30 h, hydro-thermal reaction use deionized water rinsing after terminating, are then freeze-dried 11-13h, produce multi-functional The biodegradable water-oil separationg film of application.
- 2. a kind of preparation method of the biodegradable water-oil separationg film of multifunctional application according to claim 1, it is special Sign is：The step（3）, the TiO 2 precursor used in hydro-thermal reaction is the fourth fat of metatitanic acid four, isopropyl titanate, four One kind in titanium chloride or titanium potassium oxalate.
- 3. a kind of preparation method of the biodegradable water-oil separationg film of multifunctional application according to claim 1, it is special Sign is：The step（3）, the nitrogen-containing material that uses in hydro-thermal reaction is ammoniacal liquor, melamine, urea, ammonium chloride, hydrazine, salt One kind in sour guanidine or triethylamine.
- 4. a kind of preparation method of the biodegradable water-oil separationg film of multifunctional application according to claim 1, it is special Sign is：The step（3）, the solvent of hydro-thermal reaction is in aqueous hydrochloric acid solution, aqueous hydrogen peroxide solution or glycerol-alcohol solution One kind.
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