CN110201551A - For the self-cleaning nona cellulose membrane of water-oil separating, preparation method and applications - Google Patents
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- CN110201551A CN110201551A CN201910380469.5A CN201910380469A CN110201551A CN 110201551 A CN110201551 A CN 110201551A CN 201910380469 A CN201910380469 A CN 201910380469A CN 110201551 A CN110201551 A CN 110201551A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
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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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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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
- 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
- B01D71/12—Cellulose derivatives
- B01D71/14—Esters of organic acids
- B01D71/16—Cellulose acetate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention discloses a kind of preparation methods of self-cleaning nona cellulose membrane for water-oil separating, the following steps are included: cellulose acetate film is placed in dopamine buffer solution, mechanical oscillation reaction, the cellulose membrane of poly-dopamine cladding is obtained, and the cellulose membrane of poly-dopamine cladding is subjected to vacuum drying；The cellulose membrane that poly-dopamine coats is placed in nano-cellulose dispersion liquid, reaction obtains self-cleaning nona cellulose membrane, and self-cleaning nona cellulose membrane is carried out vacuum drying.Self-cleaning nona cellulose membrane prepared by the present invention have excellent resistance tocrocking, can high efficiency separate oil-in-water emulsion, dyestuff waste liquid, stability is good, is resistant to complicated soda acid, hypersaline environment.In addition, the preparation method is simple, operability is extremely strong, and do not need to add other solvents during the preparation process, be conducive to environmental protection, to reduce the production cost of enterprise, is conducive to the large-scale application of the large-scale production and actual environment of enterprise.
Description
Technical field
The present invention relates to the technical field of nanofiber membrane modifying, specifically, refer to it is a kind of for water-oil separating from
Clean nano-cellulose film, preparation method and applications.
Background technique
For the wastewater problem got worse, such as industrial discharge of frequent oil extraction activity and oily waste water, water-oil separating
Problem one of has been a hot spot of research.Therefore, there is an urgent need to efficient oily water separation techniques.
Current method for purifying water includes chemocoagulation, solvent extraction, ion exchange, absorption, UF membrane etc..But it is traditional
The effect for carrying out water-oil separating using film is often bad, is primarily due to oil absorption and is deposited in the surface of film, to reach
There is serious dirt on film, and then causes the separating property of film and Duration that irreversible decline all occurs.
Therefore it is particularly significant to solve membrane pollution problem.In addition, sewage is not only oily waste water, but will have containing dyestuff
Waste water, and some adverse circumstances are inevitably encountered in treatment process, but existing film is difficult in these severe extreme conditions
Lower normal use, while the existing technical process for preparing film is many and diverse, more interstitial impurity can be generated in preparation process, to environment
Also unfriendly, and cost is also relatively high.
Summary of the invention
The present invention provides a kind of for the self-cleaning nona cellulose membrane of water-oil separating, preparation method and applications, is used for
Solution exists in the prior art:
The existing preparation method for preparing film is more and complicated, especially more cumbersome in technique, but production efficiency but ten
It is point low, and cost also relatively large technical problem.
When separating waste water greasy dirt, exist not can efficiently separate the film of existing preparation, and film is during the separation process since oil is inhaled
It echos sedimentation and accumulates the technical issues of forming serious dirt and then influencing membrane separating property on the surface of the film.
The first purpose of this invention is to provide a kind of preparation of self-cleaning nona cellulose membrane for water-oil separating
Method, the preparation method is simple, operation is easy, and the cost of enterprise is few, and preparation process is not required to addition more multi-solvent, green ring
It protects, can produce on a large scale；
Second object of the present invention is to provide a kind of self-cleaning nona cellulose membrane for water-oil separating, of the invention
The film of offer can enhance the hydrophily of film surface, can improve the stain resistance of film, while the separating property of film can be improved,
Extend the service life of film.
Third object of the present invention is to provide a kind of application of self-cleaning nona cellulose membrane for water-oil separating.
The film is mainly used in the field of water-oil separating.
The first purpose of this invention is achieved in that
A kind of preparation method of the self-cleaning nona cellulose membrane for water-oil separating, the present invention is by the following technical programs
It realizes: the following steps are included:
Cellulose acetate film is placed in containing in dopamine buffer solution, mechanical oscillation, reaction obtains poly-dopamine cladding
Cellulose membrane, and by poly-dopamine cladding cellulose membrane carry out vacuum drying；
The cellulose membrane that poly-dopamine coats is placed in nano-cellulose dispersion liquid, reaction obtains self-cleaning nona fiber
Plain film, and self-cleaning nona cellulose membrane is subjected to vacuum drying.
In order to preferably realize the present invention, further, the preparation step of the dopamine buffer solution are as follows: by dopamine
It is added in hydroxymethyl aminomethane hydrochloride buffer, stirs to get dopamine buffer solution.
In order to preferably realize the present invention, further, the aperture of the cellulose acetate film is 0.22 micron.
In order to preferably realize the present invention, further, cellulose acetate film is placed in containing in dopamine buffer solution,
Mechanical oscillation, reaction obtain the cellulose membrane of poly-dopamine cladding, the reaction condition are as follows: temperature is 25~90 DEG C, PH is 8.5 and
The mechanical oscillation time is 12~48h；Preferable temperature is 50 DEG C, and the time is for 24 hours.
In order to preferably realize the present invention, further, the cellulose membrane that poly-dopamine coats is placed in nano-cellulose
In dispersion liquid, reaction obtains self-cleaning nona cellulose membrane, the reaction condition: temperature is 25~70 DEG C and the mechanical oscillation time is
12~48h；Preferable temperature is 70 DEG C, and the time is for 24 hours.
In order to preferably realize the present invention, further, nano-cellulose dispersion liquid the preparation method comprises the following steps: taking nanofiber
Plain gel is placed in deionized water, and ultrasonic disperse obtains nanofiber dispersion liquid.
In order to preferably realize the present invention, further, the concentration of the nano-cellulose dispersion liquid is 1~3%.
It further include step further to preferably realize the present invention
The cellulose membrane that obtained poly-dopamine coats is placed in oscillation cleaning in deionized water, then carries out vacuum drying；
Obtained nano-cellulose film is placed in oscillation cleaning in deionized water, then carries out vacuum drying.
Second object of the present invention is fine for the self-cleaning nona of water-oil separating as made from method made above
Tie up plain film.
Third object of the present invention is in the self-cleaning nona cellulose membrane that will be used for water-oil separating in water-oil separating
Using.
The present invention provides a kind of self-cleaning nona cellulose membrane, is coated by nano-cellulose dispersion liquid and poly-dopamine
Cellulose membrane it is modified be made, with regard to existing water-oil separating for, traditional film based on polymer is typically due to oil absorption and sinks
Drop leads to serious dirt on the surface, this causes the separating property of film and Duration that irreversible decline occurs.
In long-term research process, increase the hydrophily of film surface, can effectively improve its stain resistance, so as to
To extend the service life of film.Therefore the present invention is by modified obtained nano-cellulose film, the structure with nano lamellar,
And there are the coarse structures that hydroxyl very rich and nanometer are layered for film surface, and then the film is caused not only to have Superhydrophilic
With underwater oleophobic property, better resistance tocrocking is had more, and then extends the service life of film.
The present invention is by preparing the cellulose membrane of nano-cellulose dispersion liquid and poly-dopamine cladding, and by poly-dopamine packet
The cellulose membrane covered is placed in reaction in nano-cellulose dispersion liquid and obtains self-cleaning nona cellulose membrane, from above-mentioned preparation method mistake
It can be concluded that, this preparation method does not need to add extra solvent in journey, can effectively reduce the pollution of environment, and the present invention
Preparation method simple possible, operability it is extremely strong.
The beneficial effects of the present invention are:
The present invention passes through the cellulose membrane for first preparing nano-cellulose dispersion liquid and poly-dopamine cladding, and by poly-dopamine
The cellulose membrane of cladding is placed in nano-cellulose dispersion liquid, is modified to film, and the preparation method is simple, operability is extremely strong,
And do not need to add other solvents during the preparation process, so that interstitial impurity will not be generated in entire production process, be conducive to ring
Border protection, to reduce the production cost of enterprise, is conducive to the large-scale production of enterprise.
The present invention by prepare nano-cellulose dispersion liquid and poly-dopamine cladding cellulose membrane, poly-dopamine is coated
Cellulose membrane be placed in nano-cellulose dispersion liquid, film is modified, obtained self-cleaning nona cellulose membrane have receives
The structure of rice stratiform, and there are the coarse structures that hydroxyl very rich and nanometer are layered for film surface, and then lead to the film not
Only there is Superhydrophilic and underwater oleophobic property, have more better resistance tocrocking.
Self-cleaning nona cellulose membrane obtained has water throughout curve, high throughput, lotion separation high through the invention
The efficient feature of efficiency, dye separation.
Using self-cleaning nona cellulose membrane oil-water separation produced by the present invention, isolated performance has relative to existing film
Biggish promotion, and isolated efficiency is also improved.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the process and its antipollution schematic diagram that the embodiment of the present invention prepares nano-cellulose film；
Its film surface of Fig. 2, which is the present invention, respectively to be obtained experimental example and comparative example by X-ray energy spectrum analyzer sample
Elemental analysis table；
Fig. 3 is experimental example of the embodiment of the present invention and the sample electron microscope that comparative example obtains；
Fig. 4 is the infrared spectrogram for the sample that comparative example of the present invention obtains；
Fig. 5 is the infrared spectrogram for the sample that the embodiment of the present invention obtains；
Fig. 6 is contact angle and pure water flux schematic diagram under the sample water that the embodiment of the present invention and comparative example obtain；
Fig. 7 is oleophobic property schematic diagram under the sample water that the embodiment of the present invention obtains；
Fig. 8 is schematic diagram of the obtained sample of the embodiment of the present invention to the adhesiveness of oil droplet；
Fig. 9 is the schematic diagram for the sample self-cleaning mechanism that the embodiment of the present invention obtains；
Figure 10 is separation of the obtained sample of the embodiment of the present invention to the different oil-in-water emulsions for not adding surfactant
Performance schematic diagram；
Figure 11 is separation property of the obtained sample of the embodiment of the present invention to the different oil-in-water emulsions of addition surfactant
It can schematic diagram；
Figure 12 is separative efficiency schematic diagram of the obtained sample of the embodiment of the present invention to lotion；
Figure 13 is schematic diagram of the obtained sample of the embodiment of the present invention to the oil-in-water emulsion of Nano grade；
Figure 14 is schematic diagram of the obtained sample of the embodiment of the present invention to methylene blue separative efficiency；
Figure 15 is schematic diagram of the obtained sample of the embodiment of the present invention to gentian violet separative efficiency；
Figure 16 is that the sample methylene blue that the embodiment of the present invention obtains and gentian violet separate flux schematic diagram；
Figure 17 is schematic diagram of the obtained sample of the embodiment of the present invention to oil hydrosol multi-cycle separation；
Figure 18 is schematic diagram of the obtained sample of the embodiment of the present invention in different soda acid stability inferiors；
Figure 19 is schematic diagram of the obtained sample of the embodiment of the present invention in various salts stability inferior.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.The present invention being usually described and illustrated herein in the accompanying drawings is implemented
The component of example can be arranged and be designed with a variety of different configurations.
Therefore, the detailed description of the embodiment of the present invention provided in the accompanying drawings is not intended to limit below claimed
The scope of the present invention, but be merely representative of selected embodiment of the invention.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without creative efforts belongs to the model that the present invention protects
It encloses.
Embodiment 1:
A kind of self-cleaning nona cellulose membrane and preparation method thereof for water-oil separating:
S1: cellulose acetate film pre-treatment
Cellulose acetate film is cut to 2 × 2cm, and is soaked in deionized water and is cleaned for use.
S2: configuration dopamine buffer solution
Dopamine is added in hydroxymethyl aminomethane hydrochloride buffer, dopamine buffer solution is stirred to get.
S3: the cellulose membrane of preparation poly-dopamine cladding
Cellulose acetate film obtained in S1 is placed in S2 and is obtained in dopamine buffer solution, 25 DEG C of constant temperature vibrations are placed in
Reaction 12h, PH 8.5 in water-bath is swung to take out after reaction and be washed with deionized water unreacted dopamine, then
It is transferred in 25 DEG C of vacuum tank and is dried, obtain the cellulose membrane of poly-dopamine cladding.
S4: configuration nano-cellulose dispersion liquid
The nanofiber hydrogel for weighing certain mass is placed in deionized water, and ultrasonic disperse 40min is configured to quality
Score obtains nano-cellulose dispersion liquid, set aside for use for 1%.
S5: configuration nano-cellulose film
The cellulose membrane for the poly-dopamine cladding that S3 is obtained is placed in the nanofiber dispersion liquid configured in S4, is placed in
12h is reacted in 25 DEG C of constant temperature oscillation water-baths, after reaction, is drawn off, then is placed in deionized water oscillation cleaning to go
It except unreacted nano-cellulose, then is drawn off, and then is transferred to again into 25 DEG C of vacuum drying ovens and is dried, obtain self-cleaning nona
Cellulose membrane.
Embodiment 2:
A kind of self-cleaning nona cellulose membrane and preparation method thereof for water-oil separating:
S1: cellulose acetate film pre-treatment
Cellulose acetate film is cut to 2 × 2cm, and is soaked in deionized water and is cleaned for use.
S2: configuration dopamine buffer solution
Dopamine is added in hydroxymethyl aminomethane hydrochloride buffer, dopamine buffer solution is stirred to get.
S3: the cellulose membrane of preparation poly-dopamine cladding
Cellulose acetate film obtained in S1 is placed in S2 and is obtained in dopamine buffer solution, 70 DEG C of constant temperature vibrations are placed in
Swing reacted in water-bath for 24 hours, PH 8.5 takes out after reaction and is washed with deionized water unreacted dopamine, then
It is transferred in 25 DEG C of vacuum tank and is dried, obtain the cellulose membrane of poly-dopamine cladding.
S4: configuration nano-cellulose dispersion liquid
The nanofiber hydrogel for weighing certain mass is placed in deionized water, and ultrasonic disperse 40min is configured to quality
Score obtains nano-cellulose dispersion liquid, set aside for use for 2%.
S5: configuration nano-cellulose film
The cellulose membrane for the poly-dopamine cladding that S3 is obtained is placed in the nanofiber dispersion liquid configured in S4, is placed in
It reacts for 24 hours in 50 DEG C of constant temperature oscillation water-baths, after reaction, is drawn off, then be placed in deionized water oscillation cleaning to go
It except unreacted nano-cellulose, then is drawn off, and then is transferred to again into 25 DEG C of vacuum drying ovens and is dried, obtain self-cleaning nona
Cellulose membrane, the entitled CNF@PDA of sample.
Embodiment 3:
A kind of self-cleaning nona cellulose membrane and preparation method thereof for water-oil separating:
S1: cellulose acetate film pre-treatment
Cellulose acetate film is cut to 2 × 2cm, and is soaked in deionized water and is cleaned for use.
S2: configuration dopamine buffer solution
Dopamine is added in hydroxymethyl aminomethane hydrochloride buffer, dopamine buffer solution is stirred to get.
S3: the cellulose membrane of preparation poly-dopamine cladding
Cellulose acetate film obtained in S1 is placed in S2 and is obtained in dopamine buffer solution, 60 DEG C of constant temperature vibrations are placed in
Swing reacted in water-bath for 24 hours, PH 8.5 takes out after reaction and is washed with deionized water unreacted dopamine, then
It is transferred in 25 DEG C of vacuum tank and is dried, obtain the cellulose membrane of poly-dopamine cladding.
S4: configuration nano-cellulose dispersion liquid
The nanofiber hydrogel for weighing certain mass is placed in deionized water, and ultrasonic disperse 40min is configured to quality
Score obtains nano-cellulose dispersion liquid, set aside for use for 3%.
S5: configuration nano-cellulose film
The cellulose membrane for the poly-dopamine cladding that S3 is obtained is placed in the nanofiber dispersion liquid configured in S4, is placed in
It reacts for 24 hours in 60 DEG C of constant temperature oscillation water-baths, after reaction, is drawn off, then be placed in deionized water oscillation cleaning to go
It except unreacted nano-cellulose, then is drawn off, and then is transferred to again into 25 DEG C of vacuum drying ovens and is dried, obtain self-cleaning nona
Cellulose membrane.
Embodiment 4:
A kind of self-cleaning nona cellulose membrane and preparation method thereof for water-oil separating:
S1: cellulose acetate film pre-treatment
Cellulose acetate film is cut to 2 × 2cm, and is soaked in deionized water and is cleaned for use.
S2: configuration dopamine buffer solution
Dopamine is added in hydroxymethyl aminomethane hydrochloride buffer, dopamine buffer solution is stirred to get.
S3: the cellulose membrane of preparation poly-dopamine cladding
Cellulose acetate film obtained in S1 is placed in S2 and is obtained in dopamine buffer solution, 80 DEG C of constant temperature vibrations are placed in
Reaction 36h, PH 8.5 in water-bath is swung to take out after reaction and be washed with deionized water unreacted dopamine, then
It is transferred in 25 DEG C of vacuum tank and is dried, obtain the cellulose membrane of poly-dopamine cladding.
S4: configuration nano-cellulose dispersion liquid
The nanofiber hydrogel for weighing certain mass is placed in deionized water, and ultrasonic disperse 40min is configured to quality
Score obtains nano-cellulose dispersion liquid, set aside for use for 3%.
S5: configuration nano-cellulose film
The cellulose membrane for the poly-dopamine cladding that S3 is obtained is placed in the nanofiber dispersion liquid configured in S4, is placed in
36h is reacted in 70 DEG C of constant temperature oscillation water-baths, after reaction, is drawn off, then is placed in deionized water oscillation cleaning to go
It except unreacted nano-cellulose, then is drawn off, and then is transferred to again into 25 DEG C of vacuum drying ovens and is dried, obtain self-cleaning nona
Cellulose membrane.
Embodiment 5:
A kind of self-cleaning nona cellulose membrane and preparation method thereof for water-oil separating:
S1: cellulose acetate film pre-treatment
Cellulose acetate film is cut to 2 × 2cm, and is soaked in deionized water and is cleaned for use.
S2: configuration dopamine buffer solution
Dopamine is added in hydroxymethyl aminomethane hydrochloride buffer, dopamine buffer solution is stirred to get.
S3: the cellulose membrane of preparation poly-dopamine cladding
Cellulose acetate film obtained in S1 is placed in S2 and is obtained in dopamine buffer solution, 90 DEG C of constant temperature vibrations are placed in
Reaction 48h, PH 8.5 in water-bath is swung to take out after reaction and be washed with deionized water unreacted dopamine, then
It is transferred in 25 DEG C of vacuum tank and is dried, obtain the cellulose membrane of poly-dopamine cladding.
S4: configuration nano-cellulose dispersion liquid
The nanofiber hydrogel for weighing certain mass is placed in deionized water, and ultrasonic disperse 40min is configured to quality
Score obtains nano-cellulose dispersion liquid, set aside for use for 3%.
S5: configuration nano-cellulose film
The cellulose membrane for the poly-dopamine cladding that S3 is obtained is placed in the nanofiber dispersion liquid configured in S4, is placed in
48h is reacted in 60 DEG C of constant temperature oscillation water-baths, after reaction, is drawn off, then is placed in deionized water oscillation cleaning to go
It except unreacted nano-cellulose, then is drawn off, and then is transferred to again into 25 DEG C of vacuum drying ovens and is dried, obtain self-cleaning nona
Cellulose membrane.
Comparative example 1:
A kind of cellulose membrane and preparation method thereof of poly-dopamine cladding:
S1: cellulose membrane pre-treatment
Cellulose acetate film is cut to 2 × 2cm, and is soaked in deionized water and is cleaned for use.
S2: configuration dopamine buffer solution
Dopamine is added in hydroxymethyl aminomethane hydrochloride buffer, dopamine buffer solution is stirred to get.
S3: the cellulose membrane of preparation poly-dopamine cladding
Cellulose membrane obtained in S1 is placed in S2 and is obtained in dopamine buffer solution, 70 DEG C of constant temperature oscillation water are placed in
It is reacted in bath for 24 hours, after reaction, takes out and be washed with deionized water, be then transferred in 25 DEG C of vacuum and dried, obtained
The cellulose membrane coated to poly-dopamine, is named as PDA@CA for its sample.
Experimental data:
A kind of preparation method of self-cleaning nona cellulose membrane for water-oil separating provided by the present invention, wherein nanometer
The equation that cellulose is reacted with poly-dopamine is as follows:
Self-cleaning nona cellulose membrane obtained in experimental example 1~5 is selected at random, and is named as CNF@PDA, will be compared
The cellulose membrane for the poly-dopamine cladding that example obtains is named as PDA@CA.
The film-forming process of self-cleaning nona cellulose membrane and anti-pollution schematic diagram obtained by experimental example of the present invention such as institute in 1 figure
Show.
Analysis comparison is carried out for experimental example and comparative example,
1.
The sample name CNF@PDA and PDA@CA that above-mentioned experimental example and comparative example are obtained respectively by X-ray energy spectrum analyzer
Film surface element analyzed, as shown in Figure 2, the atomic percent of Cong Tuzhong element can be seen that under nitrogen element content
Drop, it was demonstrated that obtained success in terms of the self-cleaning nona fiber membrane modifying that this experimental example obtains.
2.
By using field emission scanning electron microscope, above-mentioned experimental example and comparative example are obtained respectively sample name CNF@PDA and
PDA@CA environmental microbes are analyzed, and as shown in Figure 3, the b in Fig. 3 is the Electronic Speculum that c in PDA@CA, Fig. 3 is CNF@PDA
Figure, it can be seen from the figure that the structure that self-cleaning nona cellulose membrane obtained by this experimental example has nanometer coarse, is conducive to
Improve the separating property of film.
3.
Identify the PDA@CA for the sample name that above-mentioned experimental example and comparative example obtain respectively using Fourier Transform Infrared Spectroscopy,
CNF@PDA film functional group and membrane structure property, the infrared spectrogram of PDA@CA as shown in figure 4, the infrared spectrogram of CNF@PDA such as
Shown in Fig. 5.
Absorption peak in Fig. 4 can belong to the characteristic absorption peak of cellulose acetate film.It observes according in figure in 1642cm-1
Neighbouring characteristic carbonyl (C=O) tension belt and in 3460cm-1The feature hydroxyl (- OH) tension belt at place.
The current absorption peak of Fig. 5 is in 1282cm-1, 1470cm-1And 1602cm-1It can be respectively designated as-C-OH, N-H and C=C
These peaks come from poly-dopamine.After schiff base reaction, the CNF of protonation is in 2900cm-1It is that C-H is stretched that apparent new peak, which occurs, in place
Band, 1749cm-1Be attributed to carboxylic acid C=O, which demonstrate TEMPO oxidation after cellulose C-6 oxidation, should the result shows that CNF
It is successfully introduced into film, is the basis that the performance of subsequent self-cleaning nona tunica fibrosa is established.
4.
By using contact angle test instrument (Beijing Hake, XED-SPJ), to CA, PDA CA, the CNF of preparation
PDA film surface wetability is tested.
Oil water mixture is separated by sand core filter device, filter mainly includes three parts, and top is amount
Cartridge type filter bowl, lower section are filter bowl, and centre is sand core, after film is installed, fix the CA, PDA@CA, CNF@PDA to preparation with clip
Film pure water flux is tested.
Test method are as follows: film is laid on testboard, at video camera alignment stage, it is ensured that complete picture can be captured
Face takes 4 microlitres of deionized water drops in film surface with microsyringe, and using " three-point circle " principle, measuring instrument, which automatically generates, to be connect
Feeler degree is the wetability that can determine film surface.
Pure water flux test: in two glass tubes that film is fixed in sand core filter device, effective surface area is
1.767cm 2.With the help of pump, pure water penetration testing is measured at 0.09MPa and is before test compacted film with pure water
Until flux stabilized, then by record disengaging time and calculate separation flux.
As shown in fig. 6, the water contact angle of CA, PDA@CA, CNF@PDA film is respectively 67 °, 32 °, 24 °, pure water flux difference
For 13924,12196,11320L m-2h-1, it was demonstrated that nano-cellulose is successfully prepared, and improves the wetability of film.
5.
It is obtained from clear to verify this experimental example by using contact angle test instrument (Beijing Hake, XED-SPJ)
The underwater superoleophobic property of clean nano fibrous membrane.As shown in Figure 7, it measures in different types of underwater contact angle of oil, wherein
Show that the contact angle for methylene chloride, diesel oil, hexamethylene, toluene, crude oil is all larger than 150 ° to prove that it has extraordinary underwater
Superoleophobic property.
Due to very excellent underwater superoleophobic property, the adhesiveness to oil droplet is tested.It is squeezed as shown in a in Fig. 8 in oil droplet
It is depressed into during film surface, the shape of oil droplet becomes ellipse from spherical shape.With the increase of pressure, oil droplet will be in needle point and film table
It is slided between face.It does not find significantly to deform or adhere in subsequent separation process, it was demonstrated that CNF@PDA film, which has oil, to be protruded
Underwater self-cleaning.As shown in the b in Fig. 8, in order to further prove that the oil resistant of film drips adhesiveness, when crude oil in air will be pre-
When the CNF@PDA film of wetting is immersed in the water, the oil droplet of coating completely disengages surface in a very short period of time.
The automatically cleaning mechanism of experimental example sample of the present invention is as shown in figure 9, CNF@PDA film has good water absorbing capacity, tool
There is oil resistant adhesion property, the moisture of absorption can form powerful hydrated sheath as bed course, prevent oil from directly contacting with film.
Oil water mixture is separated by sand core filter device, respectively to without surfactant at 0.9Mpa
Oil-in-water emulsion and oil-in-water emulsion containing surfactant are filtered, and oil is mutually trapped within film top, and water phase is then led to
It crosses film to flow into the filter bowl of lower section, to reach separation purpose.Oil water mixture is separated using sand core filter device, is led to
Overwriting disengaging time and calculating separation flux.
6.
Lotion and filtrate carbon content are measured using total organic carbon analyzer (Shimadzu TOC-VCPH), calculated
Separative efficiency.
Such as Figure 10, shown in 11,12, it is shown that separating property of the self-cleaning nona cellulose membrane to various lotions.
All lotions are successfully separated in a step, total organic carbon (TOC) content in various lotion filtrates < 7mg L-
1, calculated separative efficiency > 99.91%, as shown in figure 12.Diesel oil without surfactant, hexamethylene, toluene and crude oil
The corresponding separation flux of oil-in-water emulsion be respectively 8488.96,9676.47,11126.99 and 203.73Lm-2h-1。
Due to their small drop sizes and good stability, it is more difficult to which separation is by those of surfactant stabilization cream
Liquid.Therefore, prepared self-cleaning nona cellulose membrane is had rated for the various oil-in-waters cream stable by surfactant
The separating property of liquid.As shown in figure 11, the permeation flux of diesel oil, hexamethylene, toluene and crude oil is respectively 3395.59,
4525.44,2073.01 and 149.41Lm-2h-1.Meanwhile the TOC content (including remaining surfactant) in filtrate from
17mg L-1Slightly increase to 60mg L-1, show that separative efficiency is stablized.
7.
Optical microphotograph test is carried out to emulsion and filtrate using microscope, test result shows do not have oil droplet in filtrate,
Prove that film can efficiently separate surfactant stabilized oil-in-water lotion.As shown in figure 13.
8.
Using ultraviolet specrophotometer (Shimadzu, UV-1800), to verify film absorption dyestuff ability.Such as Figure 14,15 institutes
Show, absorbance test is carried out to the methylene blue after the separation of self-cleaning nona cellulose membrane, rough gentian purple dye filtrate, calculates its suction
Attached efficiency is respectively 99.07%, 98.02%.Such as Figure 16, while disengaging time is recorded, calculates it and separate flux and be respectively
11038,11215L m-2h-1, it was demonstrated that the present invention, which prepares film, has efficiently quickly separation waste water from dyestuff.
By the loop test of multiple oil hydrosol, as shown in figure 17, self-cleaning nona cellulose membrane is recycled
Separation test, after 5 filterings, after pure water cleans, there is no significant changes for flux, illustrate the reusable of film
Property.
The stability of self-cleaning nona cellulose membrane performance is a key and stubborn problem for practical application,
Therefore stability of the film under different soda acids, various salts is determined.As shown in figure 18, the self-cleaning nona cellulose of preparation
Film impregnates 48h in the solution that pH is 2-12 respectively, and there is no significant changes for the wetability of film.
Equally, as shown in figure 19, the self-cleaning nona cellulose membrane of preparation is respectively in 50mg ml-1CaCl2,KCl,NaCl,
MgSO4,NaSO448h is impregnated in solution, there is no significant changes for the wetability of film, it was demonstrated that prepared film is resistant to soda acid
And condition with high salt.
The present invention provides a kind of self-cleaning nona cellulose membranes and preparation method thereof for oil water mixture separation, lead to
It crosses above-mentioned Experimental comparison to obtain, nano-cellulose film obtained by the present invention has stronger hydrophilic in oil water separation process
Property and underwater superoleophobic property, have this effect mainly has nanometer to be layered coarse structure because automatically cleaning tunica fibrosa of the invention is poly-,
And the pollution of crude oil can be resisted containing very hydroxyl, film simultaneously, and the preparation method of the film is simple, and it is easily operated, be conducive to
Enterprise's large-scale production.
Although an embodiment of the present invention has been shown and described, it will be understood by those skilled in the art that are as follows:
A variety of change, modification, replacement and modification, the present invention can be carried out to these embodiments by not departing under the principle of the present invention and objective
Range be defined by the claims and their equivalents.
Claims (10)
1. a kind of preparation method of the self-cleaning nona cellulose membrane for water-oil separating, it is characterised in that: the following steps are included:
Cellulose acetate film is placed in containing in dopamine buffer solution, mechanical oscillation, reaction obtains the fibre of poly-dopamine cladding
Plain film is tieed up, and the cellulose membrane of poly-dopamine cladding is subjected to vacuum drying；
The cellulose membrane that poly-dopamine coats is placed in nano-cellulose dispersion liquid, reaction obtains self-cleaning nona cellulose
Film, and self-cleaning nona cellulose membrane is subjected to vacuum drying.
2. preparation method according to claim 1, it is characterised in that: the preparation step of the dopamine buffer solution are as follows:
Dopamine is added in hydroxymethyl aminomethane hydrochloride buffer, dopamine buffer solution is stirred to get.
3. preparation method according to claim 1, it is characterised in that: the aperture of the cellulose acetate is 0.22 micron.
4. preparation method according to claim 1, it is characterised in that: be placed in cellulose acetate film and buffered containing dopamine
In solution, mechanical oscillation, reaction obtains the cellulose membrane of poly-dopamine cladding, the reaction condition are as follows: temperature is 25~90 DEG C, PH
It is 12~48h for 8.5 and mechanical oscillation time.
5. preparation method according to claim 1, it is characterised in that: the cellulose membrane that poly-dopamine coats is placed in nanometer
In cellulose dispersion liquid, reaction obtains self-cleaning nona cellulose membrane, the reaction condition: temperature is 25~70 DEG C and mechanical oscillation
Time is 12~48h.
6. preparation method according to claim 1, it is characterised in that: nano-cellulose dispersion liquid the preparation method comprises the following steps: taking
Nano-cellulose gel is placed in deionized water, and ultrasonic disperse obtains nanofiber dispersion liquid.
7. preparation method according to claim 6, it is characterised in that: the concentration of the nano-cellulose dispersion liquid be 1~
3%.
8. preparation method according to claim 1, it is characterised in that: further include step
The cellulose membrane that obtained poly-dopamine coats is placed in oscillation cleaning in deionized water, then carries out vacuum drying；
Obtained nano-cellulose film is placed in oscillation cleaning in deionized water, then carries out vacuum drying.
9. described in any item obtained methods self-cleaning nona fiber obtained for being used for water-oil separating according to claim 1~8
Plain film.
10. the application according to claim 9 for the self-cleaning nona cellulose membrane of water-oil separating in water-oil separating.
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