CN106552519B - A kind of superoleophobic calcium carbonate hybrid film of super-hydrophilic and underwater and preparation method and application - Google Patents

A kind of superoleophobic calcium carbonate hybrid film of super-hydrophilic and underwater and preparation method and application Download PDF

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CN106552519B
CN106552519B CN201610635375.4A CN201610635375A CN106552519B CN 106552519 B CN106552519 B CN 106552519B CN 201610635375 A CN201610635375 A CN 201610635375A CN 106552519 B CN106552519 B CN 106552519B
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calcium
calcium carbonate
film
alginate
solution
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CN106552519A (en
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汪秀丽
袁雪
宋飞
肖倩
罗艳葵
徐晨
聂武成
王玉忠
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Sichuan University
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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
    • B01D71/74—Natural macromolecular material or derivatives thereof
    • 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
    • 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
    • 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
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • 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
    • 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
    • B01D71/02—Inorganic material
    • 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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Abstract

The present invention provides a kind of preparation methods of the superoleophobic calcium carbonate hybrid film of super-hydrophilic and underwater, this method comprises the following steps: (1) ionic calcium soln being added in alginate solution and calcium alginate gel is prepared, be stirred to form flocculation sedimentation to gained gel；(2) with stirring, carbonate solution is added into step (1) gains, obtains calcium carbonate-calcium alginate hybrid particulates；(3) step (2) gains are filtered, it is dry, obtain the superoleophobic calcium carbonate hybrid film of super-hydrophilic and underwater.Application the present invention also provides hybridized film prepared by the above method and its in water-oil separating field.Hybridized film of the invention has good flexibility and mechanical strength；Extremely low to greasy dirt adhesion strength, pollution resistance is extremely strong；The water-oil separating of high viscosity oil and the separation of oil hydrosol may be implemented.Hydridization film preparation of the present invention is simple, low in cost, and green non-pollution can be recycled, and is expected to realize large-scale production and application.

Description

A kind of superoleophobic calcium carbonate hybrid film of super-hydrophilic and underwater and preparation method and application
Technical field
The invention belongs to water-oil separationg film preparation technical fields, and in particular to a kind of superoleophobic calcium carbonate of super-hydrophilic and underwater Hybridized film and preparation method and application.
Background technique
In recent years, as rapid development of economy, the pollution of environment also increasingly sharpen, wherein greasy dirt gets over the pollution of water body More to attract people's attention.Other than water pollution caused by oil exploitation and oil leak event, sanitary sewage and various systems It makes industry such as to weave, leather, metal, food, also contains a large amount of greasy dirt in the sewage of the industries discharge such as mechanical and chemical industry, to water body Bring serious pollution.Therefore, extremely urgent to the research and development of the material and technology that can be realized water-oil separating.Currently, Numerous studies report the water-oil separating material of super-hydrophobic super-oleophylic, but there are certain defects for such " oil removing " separation material, such as Super-hydrophobic material easily loses oleophobic property energy in practical Aquo System in air, and highly viscous oil liquid easily causes film inner pore Blocking, even separate failure so as to cause the reduction of separative efficiency.In addition, the fluorine that material introduces during hydrophobically modified is easy Cause the secondary pollution of water body.Therefore, the water-oil separating material of super-hydrophobic super-oleophylic is in actual application by larger limitation.
Calcium carbonate is a kind of highly important biogenic mineral, is the main component of animal skeleton and shell.With hydrophilic, shape The advantages that looks, scale multiplicity are controllable, excellent in mechanical performance, nontoxic, the substance containing calcium carbonate often shows in nature Excellent mechanical property out, optical property, special wellability, the characteristics such as pollution resistance.From bionic angle, preparation is independent Calcium carbonate film it is very meaningful because calcium carbonate in nature often laminar structured is present in organism with independent In such as abalone shells, nacre etc. assigns body excellent mechanical performance.Adv.Mater.2011,23,2009–2014；J CRYST GROWTH2012.01.037；The documents such as Langmuir2015,31,2014-2018 have probed into independent calcium carbonate film in succession Preparation, but do not prepare the complete independent calcium carbonate film with excellent mechanical performance successfully；And preparation method is mostly CO2Gas diffusion mineralising method or LBL self-assembly method prepare time-consuming and laborious, stability, poor controllability.It can be seen that current calcium carbonate film Preparation still in the exploratory stage.
In addition, (such as silicon fluoride is grafted ceramic membrane, nanometer titanium dioxide carbon coating to existing seperation film in water-oil separating field Ceramic membrane and calcium carbonate-base PAA graft polypropylene micropore filtering film etc.) preparation process is complicated, cost is excessively high, limit its The application in the field.
Therefore, water-oil separating, with outstanding mechanical property, complete independent carbon can efficiently be carried out by preparing one kind The technical issues of sour calcium film is this field urgent need to resolve.
Summary of the invention
In view of the shortcomings of the prior art, one of the objects of the present invention is to provide a kind of superoleophobic carbonic acid of super-hydrophilic and underwater The preparation method of calcium hybridized film, this method comprises the following steps:
(1) ionic calcium soln is added in sodium alginate soln and calcium alginate gel is prepared, to gained gel into Row stir process forms flocculation sedimentation；
(2) with stirring, carbonate solution is added into step (1) gains, obtains calcium carbonate-calcium alginate hydridization Grain；
(3) step (2) gains are filtered, it is dry, obtain the superoleophobic calcium carbonate hybrid film of super-hydrophilic and underwater.
The present invention breaches CO used in research at present2The tradition side such as gas diffusion mineralising method and LBL self-assembly method Method prepares inorganic constituents with a kind of method of simple and fast and accounts for 95% or more, has good flexibility, the independent carbon of high-modulus Sour calcium-calcium alginate gel hybridized film.Gained hybridized film utilizes the hydrophily of calcium carbonate and gel and the micro-nano of calcium carbonate granule Rice characteristic, the ultra-hydrophilic surface with multiple dimensioned coarse structure is extremely low to the adhesion strength of oil droplet in water, to high viscositys such as crude oil Oil all have superpower stain resistance.When gained hybridized film of the invention carries out grease layering mixed liquor or oil hydrosol separation, It can reuse 30 times or more.
Preferably, the ionic calcium soln is solubility calcium saline solution, and concentration is 0.01~10M, preferably calcium chloride Aqueous solution.
Preferably, the concentration of the sodium alginate soln is 0.01~10wt%.
According to the common sense of this field, reacted using the solubility calcium saline solution of any concentration with sodium alginate soln Calcium alginate gel is obtained, only when the concentration of described two solution is above-mentioned preferred embodiment, gained calcium alginate gel Quality it is preferable.
Preferably, the carbonate solution is soluble carbonate salt aqueous solution, and concentration is 0.01~10M, preferably carbonic acid Sodium water solution.
Preferably, in the ionic calcium soln, carbonate solution and sodium alginate soln each solute mass ratio be (5~ 10): (3~5): (2~6).The ratio of the calcium alginate and calcium carbonate that obtain after reaction is too low or excessively high cannot all form a film.
Preferably, in step (1) and/or step (2), the speed of agitator of the stirring is to be at least 1000rpm.
Preferably, the calcium carbonate-calcium alginate hybrid particulates size is not more than 30 microns, and pore size is not more than 20 Micron.It is furthermore preferred that the calcium carbonate-calcium alginate hybrid particulates size is not more than 5 microns, pore size is micro- no more than 3 Rice.
As shown in the embodiment of present invention, when granular size is not more than 30 microns, and pore size is not more than 20 microns, oil The efficiency of water separation is up to 90% or more.When granular size is not more than 5 microns, and pore size is not more than 3 microns, water-oil separating Efficiency up to 99% or more.
In step (2), mixing speed can regulate and control the size of calcium carbonate granule and the size of film internal orifice dimension.
Pass through the thickness for the controllable calcium carbonate hybrid film of precipitation capacity that control filters；In the drying, drying temperature is not More than 100 DEG C.
The method further comprises the steps of: after step (3) and carries out uniform pore-creating to gained calcium carbonate hybrid film；It is preferred that , the eye diameter in the hole made is 0.01~1mm.It is worth noting that as long as the hole made can be convenient for grease layering mixing The separation of liquid, the characteristic selection that those skilled in the art can be layered mixed liquor according to separated grease are different size of Hole.
Hybridized film after pore-creating can be used for the separation of grease layering mixed liquor.The hybridized film of non-pore-creating is suitable for grease The separation of lotion.
Another object of the present invention is that providing super-hydrophilic and underwater prepared by the above method superoleophobic carbon Sour calcium hybridized film.
Another object of the present invention is that providing the gained superoleophobic calcium carbonate hybrid film of super-hydrophilic and underwater in grease The application of separation field, the water-oil separating field include the separation of grease layering mixed liquor, the separation of oil hydrosol and oil-containing The processing of sewage.
Gained hybridized film of the invention is in alkanes, alkyl halide hydro carbons, ethers, benzene and derivative, ketone, gasoline, diesel oil, food With showing good stability in oil and a variety of organic phases such as crude oil, and there is good separation effect to its oil water mixture Fruit.
Beneficial effects of the present invention:
1, the preparation method of calcium carbonate hybrid film of the present invention is simple, and it is time saving and energy saving to operate；Raw material is cheap and easy to get, nontoxic nothing Evil, green non-pollution can carry out large-scale production and application；
2, calcium carbonate hybrid film of the present invention is using inorganic carbonate calcium particle as skeleton, itself has good flexibility and excellent Mechanical strength；The size in intramembranous particles and aperture can be adjusted as needed；The thickness of film also can be adjusted arbitrarily as needed Section；
3, calcium carbonate hybrid film of the present invention has the superoleophobic characteristic of super-hydrophilic and underwater, extremely low to oil droplet adhesion strength under water, Stain resistance is strong, can also show excellent antifouling property to highly viscous oils such as crude oil etc.；It can be realized a variety of oils Grease is layered the separation of mixed liquor and oil hydrosol, has very high separative efficiency；Stability in use is good, can carry out repeatedly It is recycled.
Detailed description of the invention
Fig. 1 is the SEM figure of the cross section of calcium carbonate hybrid film of the present invention, and scale is 100 μm；Illustration is display calcium carbonate film The superoleophobic optics picture of super-hydrophilic and underwater；
Fig. 2 is the SEM figure of calcium carbonate hybrid film surface of the present invention, and scale is 100 μm；Illustration is that display calcium carbonate film is super Hydrophilic and underwater superoleophobic optics picture；
Fig. 3 is calcium carbonate hybrid film of the present invention under water to the optics picture of oil droplet adhesion strength test；
Fig. 4 is the optics picture that calcium carbonate hybrid film of the present invention tests crude oil antifouling property；
Fig. 5 is oil hydrosol separator figure；
Fig. 6 is grease layering mixing liquid separating apparatus figure；
Fig. 7 is the optical photograph of oil hydrosol separation front and back.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that following embodiment is only used It is further detailed in the present invention, should not be understood as limiting the scope of the invention, which is skilled in technique Some nonessential modifications and adaptations that personnel are made according to foregoing invention content, still fall within protection scope of the present invention.
Embodiment 1
The CaCl for being 0.1M by 50g concentration2Solution is added in the sodium alginate soln that 50g concentration is 0.05wt%, shape At calcium alginate gel；Flocculent deposit is formed under 1000rpm speed of agitator；50g concentration is added under 1000rpm speed of agitator For the Na of 0.05M2CO3Solution, reaction obtain calcium carbonate-calcium alginate hybrid particulates；Sediment is filtered by vacuum, 30 DEG C Lower drying obtains independent calcium carbonate-calcium alginate gel hybridized film.
The crystal form of calcium carbonate is based on calcite in the film being prepared under this condition.Calcium carbonate granule size is 10~30 μm, pore size is 5~20 μm.Water flux is 20000 ± 26Lm-2·h-1.Oil hydrosol separative efficiency be 90.00 ± 0.09%.The film stretching modulus is 1.00 ± 0.08GPa；Bending modulus is 1.1 ± 0.1GPa.
Embodiment 2
The CaCl for being 0.1M by 50g concentration2Solution is added in the sodium alginate soln that 50g concentration is 0.05wt%, shape At calcium alginate gel；Flocculent deposit is formed under 10000rpm speed of agitator；It is dense that 50g is added under 15000rpm speed of agitator Degree is the Na of 0.05M2CO3Solution, reaction obtain calcium carbonate-calcium alginate hybrid particulates；Sediment is filtered by vacuum, 30 It is dry at DEG C, obtain independent calcium carbonate-calcium alginate gel hybridized film.
The crystal form of calcium carbonate is based on calcite in the film being prepared under this condition.Calcium carbonate granule size is 1~5 μ M, pore size are 1~3 μm.Water flux is 10000 ± 20Lm-2·h-1.Oil hydrosol separative efficiency be 99.00 ± 0.05%.The film stretching modulus is 1.15 ± 0.11GPa；Bending modulus is 1.2 ± 0.12GPa.
Embodiment 3
The CaCl for being 0.1M by 50g concentration2Solution is added in the sodium alginate soln that 50g concentration is 0.05wt%, shape At calcium alginate gel；Flocculent deposit is formed under 15000rpm speed of agitator；It is dense that 50g is added under 30000rpm speed of agitator Degree is the Na of 0.05M2CO3Solution, reaction obtain calcium carbonate-calcium alginate hybrid particulates；Sediment is filtered by vacuum, 30 It is dry at DEG C, obtain independent calcium carbonate-calcium alginate gel hybridized film.
The crystal form of calcium carbonate is based on calcite in the film being prepared under this condition.Calcium carbonate granule size is 500nm ~3 μm, pore size is 500nm~2 μm.Water flux is 7000 ± 17Lm-2·h-1.Oil hydrosol separative efficiency is maintained at 99.99% or more.The film stretching modulus is 1.23 ± 0.09GPa；Bending modulus is 1.4 ± 0.15GPa.
Embodiment 4
The CaCl for being 0.2M by 50g concentration2Solution is added in the sodium alginate soln that 50g concentration is 0.025wt%, Form calcium alginate gel；Flocculent deposit is formed under 20000rpm speed of agitator；50g is added under 20000rpm speed of agitator Concentration is the Na of 0.05M2CO3Solution, reaction obtain calcium carbonate-calcium alginate hybrid particulates；Sediment is filtered by vacuum, It is dry at 30 DEG C, obtain independent calcium carbonate-calcium alginate gel hybridized film.
Based on ball aragonite, pattern is the crystal form of calcium carbonate with porous spherical particle in the film being prepared under this condition It is main.Gel content between particle is less.Water flux is 10000 ± 25Lm-2·h-1.The film stretching modulus be 1.35 ± 0.09GPa；Bending modulus is 1.5 ± 0.1GPa.
Embodiment 5
The CaCl for being 0.1M by 50g concentration2Solution is added in the sodium alginate soln that 50g concentration is 0.04wt%, shape At calcium alginate gel；Flocculent deposit is formed under 20000rpm speed of agitator；It is dense that 50g is added under 20000rpm speed of agitator Degree is the Na of 0.05M2CO3Solution, reaction obtain calcium carbonate-calcium alginate hybrid particulates；Sediment is filtered by vacuum, 30 It is dry at DEG C, obtain independent calcium carbonate-calcium alginate gel hybridized film.
Based on ball aragonite, pattern is the crystal form of calcium carbonate with porous spherical particle in the film being prepared under this condition It is main.Gel content between particle is moderate.Water flux is 8000 ± 19Lm-2·h-1.The film stretching modulus be 0.95 ± 0.06GPa；Bending modulus is 1.2 ± 0.14GPa.
Embodiment 6
The CaCl for being 0.2M by 50g concentration2Solution is added in the sodium alginate soln that 50g concentration is 0.1wt%, shape At calcium alginate gel；Flocculent deposit is formed under 20000rpm speed of agitator；It is dense that 50g is added under 20000rpm speed of agitator Degree is the Na of 0.05M2CO3Solution, reaction obtain calcium carbonate-calcium alginate hybrid particulates；Sediment is filtered by vacuum, 30 It is dry at DEG C, obtain independent calcium carbonate-calcium alginate gel hybridized film.
Based on ball aragonite, pattern is the crystal form of calcium carbonate with porous spherical particle in the film being prepared under this condition It is main.Gel content between particle is more.Water flux is 6000 ± 15Lm-2·h-1.The film stretching modulus be 0.68 ± 0.05GPa；Bending modulus is 0.9 ± 0.1GPa.
Embodiment 7
The CaCl for being 0.1M by 50g concentration2Solution is added in the sodium alginate soln that 50g concentration is 0.05wt%, shape At calcium alginate gel；Flocculent deposit is formed under 20000rpm speed of agitator；It is dense that 50g is added under 20000rpm speed of agitator Degree is the Na of 0.05M2CO3Solution, reaction obtain calcium carbonate-calcium alginate hybrid particulates；Sediment is filtered by vacuum, 30 It is dry at DEG C, obtain independent calcium carbonate-calcium alginate gel hybridized film.
The film being prepared under this condition with a thickness of 200 μm.This thickness is suitable for the separation of oil hydrosol.The film stretching Modulus is 1.20 ± 0.10GPa (measurement of microtensile machine)；Bending modulus is that 1.6 ± 0.1GPa (survey by miniature three-point bending instrument It is fixed).
Embodiment 8
The CaCl for being 0.4M by 50g concentration2Solution is added in the sodium alginate soln that 50g concentration is 0.2wt%, shape At calcium alginate gel；Flocculent deposit is formed under 20000rpm speed of agitator；It is dense that 50g is added under 20000rpm speed of agitator Degree is the Na of 0.2M2CO3Solution, reaction obtain calcium carbonate-calcium alginate hybrid particulates；Sediment is filtered by vacuum, 30 DEG C Lower drying obtains independent calcium carbonate-calcium alginate gel hybridized film.
The film being prepared under this condition with a thickness of 1mm.With pore-creating device on calcium carbonate hybrid film equably pore-creating, hole Eye diameter is 0.5mm.Separation suitable for grease layering mixed liquor.The film stretching modulus is 1.14 ± 0.06GPa；Bending modulus For 1.3 ± 0.1GPa.
Embodiment 9
The CaCl for being 0.8M by 50g concentration2Solution is added in the sodium alginate soln that 50g concentration is 0.4wt%, shape At calcium alginate gel；Flocculent deposit is formed under 20000rpm speed of agitator；It is dense that 50g is added under 20000rpm speed of agitator Degree is the Na of 0.4M2CO3Solution, reaction obtain calcium carbonate-calcium alginate hybrid particulates；Sediment is filtered by vacuum, 30 DEG C Lower drying obtains independent calcium carbonate-calcium alginate gel hybridized film.
The film being prepared under this condition with a thickness of 2mm.The film stretching modulus is 1.05 ± 0.08GPa；Bending modulus For 1.5 ± 0.1GPa.
Embodiment 10
Ca (the NO for being 0.1M by 50g concentration3)2Solution is added in the sodium alginate soln that 50g concentration is 0.05wt%, Form calcium alginate gel；Flocculent deposit is formed under 15000rpm speed of agitator；50g is added under 30000rpm speed of agitator Concentration is the Na of 0.05M2CO3Solution, reaction obtain calcium carbonate-calcium alginate hybrid particulates；Sediment is filtered by vacuum, It is dry at 30 DEG C, obtain independent calcium carbonate-calcium alginate gel hybridized film.
The crystal form of calcium carbonate is based on calcite in the film being prepared under this condition.Calcium carbonate granule size is 500nm ~3 μm, pore size is 500nm~2 μm.Water flux is 7000 ± 17Lm-2·h-1.Oil hydrosol separative efficiency is maintained at 99.99% or more.The film stretching modulus is 1.20 ± 0.09GPa；Bending modulus is 1.3 ± 0.15GPa.
Embodiment 11
The CaCl for being 0.1M by 50g concentration2Solution is added in the sodium alginate soln that 50g concentration is 0.05wt%, shape At calcium alginate gel；Flocculent deposit is formed under 15000rpm speed of agitator；It is dense that 50g is added under 30000rpm speed of agitator Degree is the K of 0.05M2CO3Solution, reaction obtain calcium carbonate-calcium alginate hybrid particulates；Sediment is filtered by vacuum, 30 DEG C Lower drying obtains independent calcium carbonate-calcium alginate gel hybridized film.
The crystal form of calcium carbonate is based on calcite in the film being prepared under this condition.Calcium carbonate granule size is 500nm ~3 μm, pore size is 500nm~2 μm.Water flux is 7000 ± 17Lm-2·h-1.Oil hydrosol separative efficiency is maintained at 99.99% or more.The film stretching modulus is 1.25 ± 0.10GPa；Bending modulus is 1.2 ± 0.13GPa.
Embodiment 12
Ca (the NO for being 0.1M by 50g concentration3)2Solution is added in the sodium alginate soln that 50g concentration is 0.05wt%, Form calcium alginate gel；Flocculent deposit is formed under 15000rpm speed of agitator；50g is added under 30000rpm speed of agitator Concentration is the K of 0.05M2CO3Solution, reaction obtain calcium carbonate-calcium alginate hybrid particulates；Sediment is filtered by vacuum, 30 It is dry at DEG C, obtain independent calcium carbonate-calcium alginate gel hybridized film.
The crystal form of calcium carbonate is based on calcite in the film being prepared under this condition.Calcium carbonate granule size is 500nm ~3 μm, pore size is 500nm~2 μm.Water flux is 7000 ± 17Lm-2·h-1.Oil hydrosol separative efficiency is maintained at 99.99% or more.The film stretching modulus is 1.19 ± 0.09GPa；Bending modulus is 1.4 ± 0.14GPa.
Embodiment 13
The superoleophobic test of super-hydrophilic and underwater is carried out to calcium carbonate hybrid film obtained in Examples 1 to 9.The film is in air In water contact angle be 0, water droplet whole envelopes in 0.5s absorb, show as it is super hydrophilic, as shown in Figure 4；Gained film is submerged In water, underwater oil droplet is greater than 150 ° in the contact angle of film surface, to be underwater superoleophobic, as shown in Figure 4；Underwater droplets contact arrives It squeezes after film surface and is then promoted, oil droplet can be easily disengaged from surface, illustrate that film surface is extremely low to the adhesion strength of oil droplet, such as Fig. 3 It is shown.
Embodiment 14
Underwater oil rub resistance experiment is carried out to calcium carbonate hybrid film of the invention.As shown in figure 4, the calcium carbonate pre-wetted is miscellaneous Change film to impregnate in crude oil, then is immersed into water.Originally the glutinous greasy dirt hung on film is detached from rapidly surface, carbonic acid after meeting water Calcium hybridized film shows superpower resistance to oily stain energy.
Embodiment 15
Oil hydrosol separating experiment is carried out to calcium carbonate hybrid film of the invention, as shown in figure 5, described in case study on implementation 7 Calcium carbonate water-oil separationg film be placed in Suction filtration device, with clamp, connect vacuum pump to provide the external pressure of 0.9MPA；To pumping Oil hydrosol is toppled in filter device.The volume ratio of oil and water is 1:9 in oil hydrosol, and neopelex conduct is added Stabilizer.By the hole in film the separation of oil with water can not occur for partial size in 5~25 μm of emulsion droplet after demulsification, water phase passes through Seperation film, oil are mutually trapped, to realize effective lotion separation.Fig. 7 is that lotion separates front and back optics picture comparison.The present invention The separating effect of efficient stable is all had to the oil hydrosol of gasoline, edible oil, long chain alkane, a variety of oils such as silicone oil, can be weighed It uses 30 times or more again.
Embodiment 16
The separating experiment that grease layering mixed liquor is carried out to calcium carbonate hybrid film of the invention, as shown in fig. 6, embodiment 8 Described in calcium carbonate water-oil separationg film be placed in Suction filtration device with pore-creating device pore-creating, use clamp.Into Suction filtration device Topple over grease layering mixed liquor.Water forms one layer of liquid film in the rough surface of pore membrane and oil reservoir is isolated, and is supported by surface tension The fluid column of certain altitude.Water phase flows into receiving flask by fenestra under the effect of gravity, and oil is mutually retained by liquid film, to realize effective Water-oil separating.The present invention is to gasoline, edible oil, long chain alkane, the grease of a variety of oils such as silicone oil and highly viscous crude oil Layering mixed liquor all has the separating effect of efficient stable, and reusable 30 times or more.

Claims (10)

1. a kind of preparation method of the superoleophobic calcium carbonate hybrid film of super-hydrophilic and underwater, which is characterized in that the method includes such as Lower step:
(1) ionic calcium soln is added in alginate solution and calcium alginate gel is prepared, gained gel is stirred It mixes processing and forms flocculation sedimentation；
(2) with stirring, carbonate solution is added into step (1) gains, obtains calcium carbonate-calcium alginate hybrid particulates；
(3) step (2) gains are filtered, it is dry, obtain the superoleophobic calcium carbonate hybrid film of super-hydrophilic and underwater；
The carbonate solution is soluble carbonate salt aqueous solution, and saturated concentration concentration below is applicable in.
2. satisfying the method according to claim 1, wherein the ionic calcium soln is solubility calcium saline solution It is applicable in concentration concentration below；And/or the alginate includes alginate or the fruit that gel can be formed with calcium ion Glue, described to form the alginate of gel with calcium ion include sodium alginate, ammonium alginate, the alginate solution it is dense Degree can dissolve in concentration range at it and be applicable in.
3. method according to claim 1 or claim 2, which is characterized in that the ionic calcium soln, carbonate solution and alginate The mass ratio of each solute is (5~10): (3~5): (2~6) in solution.
4. the method according to claim 1, wherein in step (1) and/or step (2), the stirring of the stirring Revolving speed is at least 1000rpm.
5. the method according to claim 1, wherein being regulated and controled by speed of agitator, the calcium carbonate-calcium alginate The size of hybrid particulates is not more than 50 microns, and pore size is not more than 30 microns.
6. according to the method described in claim 5, it is characterized in that, the calcium carbonate-calcium alginate hybrid particulates size not Greater than 5 microns, pore size is not more than 3 microns.
7. the method according to claim 1, wherein drying temperature is no more than 100 DEG C in the drying.
8. the method according to claim 1, wherein the method after step (3), further comprises the steps of: pair Gained calcium carbonate hybrid film carries out uniform pore-creating, and the eye diameter in the hole made is 0.01~1mm.
9. the superoleophobic calcium carbonate hybrid film of super-hydrophilic and underwater that any one of -8 the methods are prepared according to claim 1.
10. the superoleophobic calcium carbonate hybrid film of super-hydrophilic and underwater as claimed in claim 9 is in the application of water-oil separating field, described Water-oil separating field includes separation, the separation of oil hydrosol and the processing of oily wastewater of grease layering mixed liquor.
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