CN106853296A - A kind of oil water separation type sodium alginate/graphene oxide composite aerogel and preparation method thereof - Google Patents
A kind of oil water separation type sodium alginate/graphene oxide composite aerogel and preparation method thereof Download PDFInfo
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- CN106853296A CN106853296A CN201611263274.5A CN201611263274A CN106853296A CN 106853296 A CN106853296 A CN 106853296A CN 201611263274 A CN201611263274 A CN 201611263274A CN 106853296 A CN106853296 A CN 106853296A
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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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/405—Impregnation with polymerisable compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/04—Alginic acid; Derivatives thereof
Abstract
The present invention relates to a kind of oil water separation type sodium alginate/graphene oxide composite aerogel and preparation method thereof.A kind of preparation method of oil water separation type sodium alginate/graphene oxide composite aerogel, including sodium alginate/graphene oxide liquid mixture preparation, the preparation of uncrosslinked sodium alginate/graphene oxide composite aerogel and the preparation of oil water separation type sodium alginate/graphene oxide composite aerogel.Oil water separation type sodium alginate/graphene oxide composite aerogel of the invention, with highly porous structure and perfect 3 D stereo network, separative efficiency is high, separation rate>99.9%, and salt resistance ability is high, can be applied to the marine environment of high salt, also with good elasticity, higher mechanical strength and oil resistant pollution capacity, repeats and utilizes more than 40 times and separative efficiency does not almost decline, with good recycling ability.
Description
Technical field
The present invention relates to a kind of oil water separation type composite aerogel and preparation method thereof, and in particular to a kind of oil water separation type
Sodium alginate/graphene oxide composite aerogel and preparation method thereof, with salt tolerant, superoleophobic under water and fuel sensitivity,
Belong to biomass-based functional material preparing technical field.
Background technology
In in the past few decades, Oil spills and chemical leakage accident take place frequently, and marine environment and the ecosystem are made
Into significant damage.Thus, that how to realize oil-water in marine environment efficiently separates the topic for having turned into global concern.Oil-water
Separation belongs to the category of field of interfaces, and functional material of the exploitation with superoleophobic characteristic is that to solve this problem effectively easy
Strategy.Up to now, the material in atmosphere with superoleophobic characteristic is all modified by fluorine containing silane reagent substantially, however,
The material of fluorine functional easily loses superoleophobic property in the seawater.The unique characteristic superoleophobic under water of fish scale, is bionical structure
Build superoleophobic material such as hydrogel coating and inorganic metal oxide washcoat under water and open new window.However, using this
The maximum challenge of material is that their environmental resistance ability is poor.By long-term sea water immersion, they may be from substrate
Dilatancy is come off or be subjected to, causes it gradually to lose superoleophobic property.Additionally, there is step complexity, valency in current preparation method
The shortcomings of lattice are expensive, it is difficult to realize large-scale industrialization application.Therefore, develop cheap, salt tolerance and can give birth on a large scale
The functional material of product, realizes that oil/water is separated in marine environment, is very important.
Aeroge is a kind of solid material of high porosity, is to prepare height with relatively low density and three-dimensional net structure
The good selection of flux, efficient Oil-water separation material.Sodium alginate is a kind of natural polysaccharide, and it is present in the cell membrane of brown alga,
It is connected by β -1,4- glycosidic bonds with α-L- guluronic acids by beta-D-mannuronic acid and is made up of the fragment of different proportion
Copolymer.Research shows, the aeroge prepared by this natural biologic material, with good salt tolerance and under water superoleophobic property
Can, realizing that marine environment Oil-water separation field has huge potentiality.However, want this material of large-scale application, still need to gram
Take two obstacles：1）The relatively low problem of pure sodium alginate aeroge mechanical strength；2）It is related to the ion of complexity in preparation process
Crosslinking process, large-scale production is not utilized.It is to improve aeroge mechanical strength, an effective method is by Nano grade
Reinforcer is introduced into sodium alginate aeroge three-dimensional network.In aeroge preparation technology, such as directly by divalent ion（Such as calcium
Ion）Introducing sodium alginate soln carries out ionomer, is relatively also easy to produce anisotropic colloidal particle and sol solution heterogeneous.
Common practice is to introduce CaCO3-GDL（Glucolactone）To reduce the rate of release of calcium ion.Although this mode can
To make the sol solution for producing more uniform, but practical operation is complex.
The content of the invention
In order to overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of oil water separation type sodium alginate/oxidation
Graphene composite aerogel and preparation method thereof.The present invention is filled out graphene oxide enhancing based on sodium alginate aeroge
Material is introduced inside sodium alginate aeroge three-dimensional network, by way of simple freeze-drying and ionomer are combined, structure
A kind of sodium alginate/graphene oxide composite aerogel is built, to realize the purpose of Oil-water separation, for marine environment or oil-containing
The separation of oil-aqueous mixtures in waste water.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of oil water separation type sodium alginate/graphene oxide composite aerogel of the invention, its feature
It is preparation process as follows：
（1）The preparation of sodium alginate/graphene oxide liquid mixture：
A, prepare sodium alginate soln：Sodium alginate is dissolved in deionized water, gradually will after 800 ~ 1200rpm magnetic agitations, 1 ~ 2h
Mixing speed is reduced to 500 rpm up to it is changed into clear solution, and it is the sodium alginate soln of 1wt% ~ 4wt% that concentration is obtained；
B, ultrasonically treated concentration are the 10 ~ 20min of graphene oxide suspension of 0.5wt% ~ 3wt%, then, added to step A institutes
Obtain in sodium alginate soln, make graphene oxide be 0.5 with sodium alginate mass ratio:10~1:10,1200 ~ 2000rpm magnetic force is stirred
Mix no less than 2h, obtain sodium alginate/graphene oxide dispersion；
（2）The preparation of uncrosslinked sodium alginate/graphene oxide composite aerogel：Will be equipped with step（1）Gained sodium alginate/oxygen
The vessel of graphite alkene dispersion liquid, being put into lyophilization system carries out freeze-drying, acquires uncrosslinked sodium alginate/oxidation
Graphene composite aerogel.
（3）The preparation of oil water separation type sodium alginate/graphene oxide composite aerogel：By step（2）Gained is uncrosslinked
Sodium alginate/graphene oxide composite aerogel be placed in concentration be 2wt% ~ 4wt% calcium chloride solution in, reaction 8 ~ 12h after,
Aeroge is repeatedly rinsed using deionized water repeatedly, secondary freeze drying is then carried out, oil water separation type sodium alginate/oxygen is obtained
Graphite alkene composite aerogel.
Described sodium alginate, as main body gel forming materials；Graphene oxide, as reinforcer；Calcium chloride solution, its
In calcium ion play a part of trigger crosslinking.
In the preparation method of oil water separation type sodium alginate/graphene oxide composite aerogel of the present invention, each step is most
Good parameter is as follows：
Step（1）Described magnetic agitation optimum speed is 1000rpm, and the optimal addition concentration of graphene oxide suspension is 1
Wt%, sodium alginate soln optium concentration is 2 wt%, and described graphene oxide and sodium alginate mass ratio is 1:10, it is described
Sonication treatment time is 15min.
Step（2）The vessel are culture dish, and freeze-drying temperature is -15 °C, and absolute pressure is 400 μ bar, and freezing is dry
The dry time is 48h.
Step（3）The calcium chloride solution, optium concentration is 4 wt%, and the time for immersing ionic calcium soln is 10h.
Oil water separation type sodium alginate/graphene oxide composite aerogel of the invention is as shown in figure 1, its microscopic appearance knot
Structure is as shown in Fig. 2 in Fig. 2, a is low range micro-structure diagram（× 50,500 μm）, b is high magnification micro-structure diagram（× 1000,
10μm）；Various oil products can be such as Fig. 3 institutes in oil water separation type sodium alginate/graphene oxide composite aerogel wettability of the surface
Show.
The performance test of oil water separation type sodium alginate/graphene oxide composite aerogel of the invention, method is as follows：
（1）Wettability is tested
Water and oil are tested by contact angle using Drop Shape Analysis System and are estimated in aeroge wettability of the surface energy.
Air reclaimed water and oil can be tested in aeroge wettability of the surface：
5 μ L water droplets and oil droplet are taken respectively（Test oil is：Kerosene, pumping fluid, n-hexane, soybean oil and toluene）Instill aeroge
Surface, the contact angle for tracking water droplet and oil droplet using Drop Shape Analysis System changes, and assesses its aerial wetability.
Oil can be tested in aeroge wettability of the surface under water：
Aeroge is immersed into simulated seawater, be dissolved in 17.2 g sea salt in 500 mL deionized waters by the simulated seawater, used
Micro syringe is by 5 μ L oil droplets（Test oil is：Kerosene, pumping fluid, n-hexane, soybean oil and toluene）From aeroge bottom surface
Injection, assesses oily in aeroge wettability of the surface under water by the size for testing oil droplet contact angle.
（2）Salt resistant character is tested
Aeroge is immersed 30 days in simulated seawater（It is set as a cycle）, it is once oily in aeroge under water every test in 5 days
Surface（Kerosene is taken for test oil）Wettability, i.e., the contact angle change according to oil judges the anti-salt property of aeroge.
（3）Oil-aqueous mixtures separative efficiency test
First, aeroge surface is pre-wetted with water, is then fixed between two vertical glass tubes and is pressed from both sides with clip
Firmly, liquid-collecting bottle is connect below.Configuration oil-aqueous mixtures（V:V=1:1）Apparatus above is poured into, the separative efficiency to oil water mixture is entered
Row test.Wherein, test oil product includes kerosene, pumping fluid, n-hexane, soybean oil, toluene and crude oil, and water is simulated seawater.
The separative efficiency of oil-aqueous mixtures then by calculating the quality of the front and rear oil product of filtering, is determined by below equation：
η (%) = (m a/m b) × 100
Wherein,m bWithm aThe quality of oil before and after respectively filtering,ηIt is the separative efficiency of oil-aqueous mixtures.
（4）Reusing is tested
Oil-aqueous mixtures are separated and finished, and oil water separation type sodium alginate/graphene oxide composite aerogel of the invention is carried out
Repeatedly extrude and rub, and the oil droplet of aeroge remained on surface is rinsed with the water of flowing, continue on for oil-aqueous mixtures next time
Separation process, and separative efficiency is tested.
Advantages of the present invention and beneficial effect：Compared with prior art, the beneficial effects of the invention are as follows profit of the invention
Divergence type sodium alginate/graphene oxide composite aerogel, with highly porous structure and perfect 3 D stereo network, table
Reveal excellent Oil-water separation efficiency.The aeroge also has good elasticity, higher mechanical strength and oil resistant pollution capacity,
It is repeatable that using more than 40 times, separative efficiency does not almost decline.
Advantages of the present invention is as follows：
（1）Oil water separation type sodium alginate/graphene oxide composite aerogel of the invention, with highly porous structure, this
Structure is planted through whole three-dimensional network, is conducive to the separation of oil-aqueous mixtures, separative efficiency>99.9%, separative efficiency is high.
（2）Oil water separation type sodium alginate/graphene oxide composite aerogel of the invention, with salt tolerant energy higher
Power, has expanded the scope of application of the aeroge in Oil-water separation field, can be applied to the marine environment of high salt.
（3）Oil water separation type sodium alginate/graphene oxide composite aerogel of the invention, with good elasticity and machine
Tool intensity, can restore to the original state rapidly and structure is without prejudice through repeatedly rubbing, extruding, and be conducive to the multiple circulation of aeroge
Recycle.
（4）Oil water separation type sodium alginate/graphene oxide composite aerogel of the invention, with superoleophobic property under water
Can, oily contact angle is up to 166 °, is demonstrated by the oil resistant pollution capacity of uniqueness.Oil-aqueous mixtures are separated and finished, aeroge surface
Without chemical reagent treatment, only needing clear water to rinse can just be continuing with the oil droplet of residual, with good recycling ability.
Present invention selection is added into very good mechanical properties and the graphene oxide of notable flexibility as reinforcer
Sodium alginate soln, prepares compound sodium alginate/graphene oxide composite aerogel, and the introducing of graphene oxide can be effective
The load that transfer sodium alginate matrix in ground is born, can build the more excellent three-dimensional network skeleton of mechanical performance.Meanwhile, the present invention
A kind of simpler preparation technology is proposed, i.e., is not first handed over sodium alginate/graphene oxide mixed solution freeze-drying
The composite aerogel skeleton structure of connection, then, is dipped in CaCl2The aqueous solution is cleaned with carrying out rapid ionomer reaction
Fall unnecessary Ca2+Afterwards, then secondary freeze drying is carried out.The method make full use of fast reaction between sodium alginate and calcium ion from
And harden porous sodium alginate/graphene oxide compound skeleton structure.
Brief description of the drawings
Fig. 1 is oil water separation type sodium alginate/graphene oxide composite aerogel pictorial diagram.
Fig. 2 is oil water separation type sodium alginate/graphene oxide composite aerogel microscopic appearance figure,（a）For low range is micro-
See structure chart（× 50,500 μm）,（b）High magnification micro-structure diagram（× 1000,10 μm）.
The various oil products of Fig. 3 are in oil water separation type sodium alginate/graphene oxide composite aerogel wettability of the surface energy（Connect
Feeler）, wherein, abscissa represents the species of test oil product, and ordinate represents contact angle size.
Specific embodiment
In order to fully disclose oil water separation type sodium alginate/graphene oxide composite aerogel of the invention and its preparation side
Method, is described in further detail with reference to embodiment to the present invention.
The preparation method of embodiment 1, a kind of oil water separation type sodium alginate/graphene oxide composite aerogel, including with
Lower step：
（1）The preparation of sodium alginate/graphene oxide liquid mixture：
A, prepare sodium alginate soln：Sodium alginate is dissolved in deionized water, 1000rpm magnetic agitations will gradually be stirred after 1 hour
Mix speed and be reduced to 500 rpm up to it is changed into clear solution, it is the sodium alginate soln of 2wt% that concentration is obtained；
B, ultrasonically treated concentration are the graphene oxide suspension 15min of 1wt%, and then, the sodium alginate added to step A is molten
In liquid, graphene oxide is set to be 1 with sodium alginate mass ratio:10,1500rpm magnetic agitation 2h, the homogeneous sodium alginate of acquisition/
Graphene oxide dispersion；
（2）The preparation of uncrosslinked sodium alginate/graphene oxide composite aerogel：
Will be equipped with step（1）The vessel of gained sodium alginate/graphene oxide dispersion, are put into lyophilization system（- 15 °C,
400μbar）Freeze-drying 48h is carried out, freeze-drying and uncrosslinked sodium alginate/graphene oxide composite aerogel is obtained；
The vessel are culture dish.
（3）The preparation of oil water separation type sodium alginate/graphene oxide composite aerogel：
By step（2）The uncrosslinked sodium alginate of gained/graphene oxide composite aerogel is placed in calcium chloride solution（Concentration is
4wt%）Middle 10h, fully to carry out the reaction of calcium ion crosslinking；After reaction, aeroge is repeatedly rinsed using deionized water repeatedly,
To remove uncrosslinked calcium ion, secondary freeze drying is then carried out again, obtain oil water separation type sodium alginate/graphene oxide
Composite aerogel.
Oil water separation type sodium alginate/graphene oxide composite aerogel prepared by embodiment 1, by following test：
（1）Wettability is tested
Water and oil can be tested by contact angle using Drop Shape Analysis System in aeroge wettability of the surface and is estimated.
Air reclaimed water and oil can be tested in aeroge wettability of the surface：5 μ L water droplets and oil droplet are taken respectively（Test oil is：Kerosene, vacuum
Pump oil, n-hexane, soybean oil and toluene）Aeroge surface is instilled, the contact angle of water is tracked using Drop Shape Analysis System
（WCA）And the contact angle of oil（OCA）Change, assesses its aerial wetability.
Result shows that water droplet and oil droplet rigid connection touch aeroge surface, just penetrate into inside aeroge quickly, are demonstrated by high
Super hydrophilic and super oil-wet behavior, water and oil contact angle be 0 °.
Oil can be tested in aeroge wettability of the surface under water：Aeroge is immersed into simulated seawater, with micro syringe by 5
μ L oil droplets（Test oil is：Kerosene, pumping fluid, n-hexane, soybean oil and toluene）From the injection of aeroge bottom surface, by test
The size assessment at droplets contact angle is oily in aeroge wettability of the surface under water.
Result shows that oil droplet sticks to the lower surface of aeroge, not any infiltration, and OCA is all more than 150 °, such as accompanying drawing
Shown in 3, extremely strong property superoleophobic under water is demonstrated by.
（2）Salt resistant character is tested
Aeroge is immersed 30 days in simulated seawater（It is set to a cycle）, it is once oily in aeroge table under water every test in 5 days
Face（It is test oil product to take kerosene）Wettability, i.e., the contact angle change according to oil judges the anti-salt property of aeroge.
Result shows, OCA is gradually reduced from 160 ° but is all higher than 150 °, illustrates that aeroge soaks 30 days in simulated seawater
Still there is state superoleophobic under water afterwards, high salt tolerance is illustrated.
（3）Oil-aqueous mixtures separative efficiency test
First, aeroge surface is pre-wetted with water, is then fixed between two vertical glass tubes and is pressed from both sides with clip
Firmly, liquid-collecting bottle is connect below.Configuration oil-aqueous mixtures（V:V=1:1）Apparatus above is poured into, the separative efficiency to oil water mixture is entered
Row test.Wherein, test oil product includes kerosene, pumping fluid, n-hexane, soybean oil, toluene and crude oil, and water is simulated seawater.
Result shows, oil water separation type sodium alginate/graphene oxide composite aerogel manufactured in the present embodiment, with compared with
Oil high-aqueous mixtures separating power, the separative efficiency to kerosene-water is up to 99.6%, to other several oil product separative efficiencies all
More than 98.5%.
（4）Reusing is tested
Oil-aqueous mixtures are separated and finished, and airsetting is combined to oil water separation type sodium alginate/graphene oxide manufactured in the present embodiment
Glue is repeatedly extruded and rubbed, and the oil droplet of aeroge remained on surface is rinsed with the water of flowing, continues on for oil-water next time
The separation process of mixture, and separative efficiency is tested.
Result shows that oil water separation type sodium alginate/graphene oxide composite aerogel manufactured in the present embodiment repeats profit
Structural failure and metaboly are not found with 40 times, illustrate that aeroge has elasticity and mechanical strength higher；Again to oil-
Aqueous mixtures separation process is tested, and aeroge still presents separative efficiency higher, up to more than 98%.
The preparation method of embodiment 2, a kind of oil water separation type sodium alginate/graphene oxide composite aerogel, including with
Lower step：
（1）The preparation of sodium alginate/graphene oxide liquid mixture：
A, prepare sodium alginate soln：Sodium alginate is dissolved in deionized water, gradually will stirring speed after 1200rpm magnetic agitations 1h
Degree is reduced to 500 rpm up to it is changed into clear solution, and it is the sodium alginate soln of 4wt% that concentration is obtained；
B, ultrasonically treated concentration are the graphene oxide suspension 15min of 0.5wt%, then, added to the sodium alginate of step A
In solution, graphene oxide is set to be 0.5 with sodium alginate mass ratio:10,2000rpm magnetic agitation 2h, obtain sodium alginate/oxygen
Graphite alkene dispersion liquid；
（2）The preparation of uncrosslinked sodium alginate/graphene oxide composite aerogel：
Will be equipped with step（1）The vessel of gained sodium alginate/graphene oxide dispersion, are put into lyophilization system（- 15 °C,
400μbar）Freeze-drying 48h is carried out, uncrosslinked sodium alginate/graphene oxide composite aerogel is obtained.
（3）The preparation of oil water separation type sodium alginate/graphene oxide composite aerogel：
By step（2）The uncrosslinked sodium alginate of gained/graphene oxide composite aerogel is placed in calcium chloride solution（Concentration is
3wt%）Middle 12h, fully to carry out the reaction of calcium ion crosslinking.After reaction, aeroge is repeatedly rinsed using deionized water repeatedly,
To remove uncrosslinked calcium ion, secondary freeze drying is then carried out again, obtain oil water separation type sodium alginate/graphene oxide
Composite aerogel.
Oil water separation type sodium alginate/graphene oxide composite aerogel prepared by embodiment 2, by following test：
（1）Wettability is tested
Air reclaimed water and oil can be tested in aeroge wettability of the surface：5 μ L water droplets and oil droplet are taken respectively（Test oil is：Kerosene,
Pumping fluid, n-hexane, soybean oil and toluene）Aeroge surface is instilled, water droplet and oil are tracked using Drop Shape Analysis System
The contact angle change of drop, assesses its aerial wetability.
Result shows that water droplet and oil droplet can be penetrated into inside aeroge quickly, shows high super hydrophilic（WCA= 0°）
With super oil-wet behavior（OCA= 0°）.
Oil can be tested in aeroge wettability of the surface under water：Aeroge is immersed into simulated seawater, with micro syringe by 5
μ L oil droplets（Test oil is：Kerosene, pumping fluid, n-hexane, soybean oil and toluene）From the injection of aeroge bottom surface, by test
The size assessment at droplets contact angle is oily in aeroge wettability of the surface under water.
Result shows that contact angle of the various oil products on aeroge surface is all more than 150 °, is demonstrated by the extremely strong water of aeroge
Under superoleophobic property.
（2）Salt resistant character is tested
Aeroge is immersed 40 days in simulated seawater（It is set to a cycle）, it is once oily in aeroge table under water every test in 5 days
Face（Kerosene is taken for test oil）Wettability, i.e., the contact angle change according to oil judges the anti-salt property of aeroge.
Result shows, as immersion number of days increases, OCA is gradually reduced from 160 ° but is all higher than 150 °, illustrates that aeroge exists
Still there is state superoleophobic under water after being soaked 40 days in simulated seawater, high salt tolerance is illustrated.
（3）Oil-aqueous mixtures separative efficiency test
First, aeroge surface is pre-wetted with water, is then fixed between two vertical glass tubes and is pressed from both sides with clip
Firmly, liquid-collecting bottle is connect below.Configuration oil-aqueous mixtures（V:V=1:1）Apparatus above is poured into, the separative efficiency to oil water mixture is entered
Row test.Wherein, test oil product includes kerosene, pumping fluid, n-hexane, soybean oil, toluene and crude oil, and water is simulated seawater.
Result shows that aeroge manufactured in the present embodiment has oil higher-aqueous mixtures separating power, to kerosene-water
Separative efficiency be up to 99.9%, 97% is above to other several oil product separative efficiencies.
（4）Reusing is tested
Oil-aqueous mixtures is separated and finished, and composite aerogel manufactured in the present embodiment is repeatedly extruded and rubbed, and with flowing
Water rinse the oil droplet of aeroge remained on surface, continue on for the separation process of oil-aqueous mixtures next time, and to separative efficiency
Tested.
Result shows that aeroge manufactured in the present embodiment is reused 30 times and do not find structural failure and metaboly,
Illustrate that aeroge has elasticity and mechanical strength higher；Oil-aqueous mixtures separation process is tested again, aeroge is still
Separative efficiency higher so is presented, up to more than 97%.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modification, should all belong to covering scope of the invention.
Claims (6)
1. a kind of preparation method of oil water separation type sodium alginate/graphene oxide composite aerogel, it is characterised in that prepare step
It is rapid as follows：
（1）The preparation of sodium alginate/graphene oxide liquid mixture：
A, prepare sodium alginate soln：Sodium alginate is dissolved in deionized water, gradually will after 800 ~ 1200rpm magnetic agitations, 1 ~ 2h
Mixing speed is reduced to 500 rpm up to it is changed into clear solution, and it is the sodium alginate soln of 1wt% ~ 4wt% that concentration is obtained；
B, ultrasonically treated concentration are the 10 ~ 20min of graphene oxide suspension of 0.5wt% ~ 3wt%, then, added to step A institutes
Obtain in sodium alginate soln, make graphene oxide be 0.5 with sodium alginate mass ratio:10~1:10,1200 ~ 2000rpm magnetic force is stirred
Mix no less than 2h, obtain sodium alginate/graphene oxide dispersion；
（2）The preparation of uncrosslinked sodium alginate/graphene oxide composite aerogel：Will be equipped with step（1）Gained sodium alginate/oxygen
The vessel of graphite alkene dispersion liquid, being put into lyophilization system carries out freeze-drying, acquires uncrosslinked sodium alginate/oxidation
Graphene composite aerogel.
2.（3）The preparation of the sodium alginate of calcium ion crosslinking/graphene oxide composite aerogel：By step（2）Gained is uncrosslinked
Sodium alginate/graphene oxide composite aerogel be placed in concentration be 2wt%-4wt% calcium chloride solution in, reaction 8-12h after,
Aeroge is repeatedly rinsed using deionized water repeatedly, secondary freeze drying is then carried out, obtain the sodium alginate of calcium ion crosslinking/
Graphene oxide composite aerogel.
3. the preparation side of a kind of oil water separation type sodium alginate/graphene oxide composite aerogel according to claim 1
Method, it is characterised in that step（1）Described magnetic agitation optimum speed is 1000rpm, and the optimal of graphene oxide suspension adds
Plus concentration is 1 wt%, sodium alginate soln optium concentration is 2 wt%, and described graphene oxide is with sodium alginate mass ratio
1:10, described sonication treatment time is 15min.
4. the preparation side of a kind of oil water separation type sodium alginate/graphene oxide composite aerogel according to claim 1
Method, it is characterised in that step（2）The vessel are culture dish, and freeze-drying temperature is -15 °C, and absolute pressure is 400 μ bar, cold
Jelly drying time is 48h.
5. the preparation side of a kind of oil water separation type sodium alginate/graphene oxide composite aerogel according to claim 1
Method, it is characterised in that step（3）The calcium chloride solution, optium concentration is 4 wt%, and the time for immersing ionic calcium soln is 10h.
6. the compound airsetting of oil water separation type sodium alginate/graphene oxide that prepared by the either method as described in claim 1-4
Glue.
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