CN109481950A - A method of the unsaturation salting liquid crystallization based on carbon-based material - Google Patents
A method of the unsaturation salting liquid crystallization based on carbon-based material Download PDFInfo
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- CN109481950A CN109481950A CN201710822861.1A CN201710822861A CN109481950A CN 109481950 A CN109481950 A CN 109481950A CN 201710822861 A CN201710822861 A CN 201710822861A CN 109481950 A CN109481950 A CN 109481950A
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- graphene oxide
- salting liquid
- solution
- sodium
- carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
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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
- B01D67/0039—Inorganic membrane manufacture
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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
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D2009/0086—Processes or apparatus therefor
Abstract
The method for the unsaturation salting liquid crystallization based on carbon-based material that the invention discloses a kind of.This method includes the following steps: for carbon-based material to be immersed in 10~120min in salting liquid, until precipitating crystal；Wherein, the salting liquid is unsaturation solution, molar concentration >=1mol/L of the salting liquid.Method preparation process of the invention is simple, easily operated, realizes and prepares crystal in normal temperature and pressure unsaturation solution, opens far below the method for preparing crystal under the conditions of saturated concentration, have a good application prospect.
Description
Technical field
The method for the unsaturation salting liquid crystallization based on carbon-based material that the present invention relates to a kind of.
Background technique
With the burgeoning population in the whole world and industrialization, freshwater resources are increasingly deficient, and the urgent status be expected to
The desalination of water purifies to obtain effectively solution (Nature 452,2008,301~310).
The carbon-based materials such as graphene oxide membrane gradually show filter membrane of new generation with its fast and accurate desalination characteristic
Potentiality (Science 343,2014,752~754；Science 333,2011,712~717；Science 332,2011,674
~676；Adv.Funct.Mater.23,2013,3693~3700；Chem.Soc.Rev.44,2015,5016~5030).Carbon
Sill is the rapid osmotic and salt ion of water in the formation and its channel of aquaporin as the vital factor of filter membrane
Retention.When hydrone penetrates into aquaporin, due to the hydrophobic effect on carbon material aromatic ring surface, can be formed almost without friction
Rapid osmotic water flow, infiltration rate several orders of magnitude higher than traditional filter membrane achieve the purpose that high efficiency filter
(Adv.Mater.28,2016,2287~2310).However when graphene oxide membrane for salting liquid infiltration screening after,
The residual (Science 343,2014,752~754) that the salting liquid of high concentration is had found in film, goes out on carbon-based material surface
The enrichment (Sci.Rep~Uk 3,2013,3436) of the salt ion of high concentration is showed.High salt concentration is enriched in aquaporin in film, has
It may cause channel block.
Currently, it is rich to cannot achieve high local concentrations salt far below the salting liquid of saturated concentration under conditions of normal temperature and pressure
Collection is so that precipitate crystal.This problems demand solves.
Summary of the invention
The technical problem to be solved by the present invention is to overcome in the prior art under conditions of normal temperature and pressure far below saturation
The defect of crystallization can not be precipitated in the salting liquid of concentration, provide a kind of side of unsaturation salting liquid crystallization based on carbon-based material
Method.Method of the invention can make unsaturated salting liquid that crystallization be precipitated at normal temperatures and pressures, achieve the purpose that the desalination purification of water.
The present invention solves above-mentioned technical problem by following technical proposals.
The method for the unsaturation salting liquid crystallization based on carbon-based material that the present invention provides a kind of comprising following step:
Carbon-based material is immersed in 10~120min in salting liquid, until precipitating crystal；Wherein, the salting liquid is non-
Saturated solution, molar concentration >=1mol/L of the salting liquid.
In the present invention, the oxidation of graphene oxide film, partial reduction that the carbon-based material preferably independently supports
Graphene film, with filter membrane support graphene oxide membrane or containing the carbon-based material of aromatic ring structure.
In the present invention, the carbon-based material is known in this field to be made by 1 drop-coating of method and/or 2 suction method of method,
The drop-coating is the drop-coating of this field routine, and the suction method is the suction method of this field routine.Preferably, the independence
The preparation method of the graphene oxide film of support preferably uses drop-coating (method 1) comprising following steps: will aoxidize stone
Black alkene solution drop coating is drying to obtain the graphene oxide membrane independently supported in smooth hydrophobic paper surface.By the independence of above-mentioned acquisition
The graphene oxide membrane of support carries out hydro-thermal reaction to get partial reduction graphene oxide membrane.
The graphene oxide with filter membrane support preferably uses suction method (method 2) comprising following steps:
Graphene oxide solution is filtered, filter membrane is drying to obtain the graphene oxide membrane with filter membrane support；Wherein, described to filter as filter
Film filters.The graphene oxide membrane that filter membrane support is had described in above-mentioned acquisition is subjected to hydro-thermal reaction to get partial reduction oxygen
Graphite alkene film.
In method 1 or method 2, the graphene oxide solution is graphene oxide solution commonly used in the art.Institute
The graphene oxide that the graphene oxide in graphene oxide solution is this field routine is stated, improvement is preferably passed through
The graphene oxide of Hummers method preparation.The solvent of the graphene oxide solution is commonly used in the art for matching
The solvent of graphene oxide solution is set, can be organic solvent or water, the organic solvent is preferably ethyl alcohol, acetone, dimethyl
Sulfoxide (DMSO) etc. can also be the mixed solvent of several organic solvents.The concentration of the graphene oxide solution is that this field is normal
The concentration of the graphene oxide solution used is advised, preferably, the mass concentration of the graphene oxide solution is 0.1~10mg/
ML is more preferably 5mg/mL.
In method 2, the filter membrane is filter membrane commonly used in the art, preferably water phase filter membrane, the hole of the filter membrane
Diameter is preferably 0.22 μm.
In method 1 or method 2, the operation of the drying and condition are the operation and condition of the drying of this field routine,
If do not damage the drying condition of the property of film, such as: in drying basin air drying, frozen drying, in baking oven
The methods of the dry drying means that can be used as film of normal-temperature vacuum, it is dry preferably in baking oven, the temperature of the drying compared with
It is goodly 60~80 DEG C, is more preferably 70 DEG C.The time of the drying is preferably 6~10 hours, is more preferably 8 hours.
In method 1 or method 2, the hydro-thermal reaction is the hydro-thermal reaction of this field routine, preferably in deionized water
Middle carry out hydro-thermal reaction.The dosage of the deionized water of the hydro-thermal reaction do not do it is specifically limited, as long as being able to carry out hydro-thermal reaction
, preferably 20~50mL is more preferably 30mL.The temperature of the hydro-thermal reaction is preferably 160~200 DEG C, more preferably
Ground is 180 DEG C.
In the present invention, flatness, thickness and the surface area size of the film of the carbon-based material will not influence crystal precipitation.Institute
The thickness for stating the film of carbon-based material is preferably 0.2 micron~100 microns, is more preferably 25 microns.
In the present invention, the carbon-based material is known in this field can vacuum oven at normal temperatures and pressures, lower than 180 DEG C
Interior or ion concentration is that the salting liquid of 0.1~5.0mol/L can save for a long time.
In the present invention, the salting liquid is salting liquid commonly used in the art, preferably potassium salt soln and/or sodium salt
Solution, example sodium salt as mentioned can be sodium sulphate, sodium carbonate, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, and the sylvite can
For potassium sulfate, potassium carbonate, potassium fluoride, potassium chloride, potassium bromide, potassium iodide；Salt in the salting liquid can also be calcium chloride, chlorination
Magnesium or ammonium chloride etc..
In the present invention, the salting liquid is preferably inorganic salt solution or organic slat solution；The inorganic salt solution
Solvent is water；The solvent of the organic slat solution is the solvent of organic slat solution commonly used in the art, such as ethyl alcohol, first
Alcohol, acetone, glycerol, dichloroethanes, trichloro ethylene, chloroform or toluene etc..
In the present invention, the salting liquid is unsaturation solution, and " unsaturation solution " this concept those skilled in the art are equal
Know that its meaning, ie in solution concentration are less than the concentration of saturated solution.The molar concentration of the salting liquid of the invention be 1mol/L extremely
The concentration of the saturated solution of the salt.
In the present invention, the molar concentration of the salting liquid is preferably 2.5mol/L.
In the present invention, the salting liquid is preferably sodium-chloride water solution, when the carbon-based material is to pass through the suction filtration
Made from method when the graphene oxide membrane of the partial reduction, the molar concentration of the sodium-chloride water solution is preferably 1.0~
4.0mol/L, such as 1.0mol/L, 1.5mol/L, 2.0mol/L, 2.5mol/L, 3.0mol/L, 4.0mol/L；When described carbon-based
When material is the graphene oxide membrane as made from the drop-coating, the molar concentration of the sodium-chloride water solution is preferably
For 2.5~4.5mol/L, such as 2.5mol/L, 4.0mol/L, 4.5mol/L.
In the present invention, the time of the immersion is preferably 0.5 hour.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that:
Method for crystallising of the invention can make unsaturated salting liquid that crystallization be precipitated at normal temperatures and pressures, and the desalination for reaching water is net
The purpose of change.
Detailed description of the invention
Fig. 1 is the graphene film in the embodiment of the present invention 1 and 2, wherein (A) is suction method preparation in the embodiment of the present invention 1
With filter membrane support graphene oxide membrane, (B) be the embodiment of the present invention 1 in suction method preparation partial reduction oxidation stone
Black alkene film, (C) are the graphene oxide membrane of drop-coating preparation in the embodiment of the present invention 2 independently supported.
Fig. 2 is that the XRD of the graphene oxide membrane of the partial reduction in the embodiment of the present invention 1 after salting liquid immersion detects figure.
Fig. 3 is the XRD detection of the graphene oxide filter membrane independently supported in the embodiment of the present invention 2 after salting liquid immersion
Figure.
Fig. 4 is that the WAXS of the graphene oxide membrane of the partial reduction in the embodiment of the present invention 1 after salting liquid immersion detects figure.
Fig. 5 is salt water, the salinity of the graphene oxide filter membrane independently supported in the embodiment of the present invention 2 after salting liquid immersion
Adsorbance and film in salinity.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
In following embodiments 1 with filter membrane support graphene oxide film, partial reduction graphene oxide membrane with
And the graphene oxide membrane independently supported in embodiment 2 is all the graphene oxide using the Hummers method preparation of improvement
It is obtained, but the graphene oxide of equally applicable other methods preparation.
Embodiment 1
The graphene oxide membrane of graphene oxide membrane and partial reduction with suction method preparation with filter membrane support.
Taking 1mL concentration is 5mg/mL graphene oxide water solution, is diluted to 10mL with deionized water, carries out filter membrane suction filtration,
It is put into the drying 8 hours of 70 DEG C of baking oven later, the graphene oxide membrane with filter membrane support can be obtained, with a thickness of 25 microns；
The preparation of partial reduction graphene oxide: above-mentioned acquisition is had to the graphene oxide membrane of filter membrane support, is put into and contains
Have and carry out 180 DEG C of hydro-thermal reactions in the reaction kettle of 30mL deionized water, partial reduction graphene oxide membrane can be obtained, with a thickness of 25
Micron.
Will with filter membrane support graphene oxide membrane be separately immersed in molar concentration be 0.25mol/L, 0.5mol/L,
In the NaCl aqueous solution of 1.0mol/L, 1.5mol/L, 2.0mol/L, 2.5mol/L, 3.0mol/L, 4.0mol/L and 5.0mol/L
It 0.5 hour, takes out carry out XRD test later, detect NaCl crystal peak.
By the graphene oxide membrane of partial reduction be separately immersed in molar concentration be 0.25mol/L, 0.5mol/L,
In the NaCl aqueous solution of 1.0mol/L, 1.5mol/L, 2.0mol/L, 2.5mol/L, 3.0mol/L, 4.0mol/L and 5.0mol/L
It 0.5 hour, takes out carry out XRD test later, detect NaCl crystal peak.
Embodiment 2
The graphene oxide membrane independently supported is prepared with drop-coating.
Taking 1mL concentration is 5mg/mL graphene oxide water solution drop coating in smooth hydrophobic paper surface, enters 70 DEG C of dryings 8 of baking oven
Hour, the graphene oxide membrane independently supported can be obtained, with a thickness of 100 microns.
By the graphene oxide membrane independently supported be separately immersed in molar concentration be 0.1mol/L, 0.25mol/L,
In the NaCl aqueous solution of 0.5mol/L, 1.0mol/L, 2.0mol/L, 2.5mol/L, 4.0mol/L, 4.5mol/L and 5.0mol/L
0.5 hour, soaking solution was removed later and is centrifuged disengaging film surface absorption water, wet film weighing is taken out, is subsequently placed into baking oven later
60 DEG C drying 6 hours, take out dry film weighing.
Calculate salting liquid, the adsorbance of salinity and film in the graphene oxide filter membrane absorption salting liquid caudacoria independently supported
Interior salinity.
Effect example 1
(1) XRD (X-ray diffraction) test result
Fig. 2 is that the XRD of the graphene oxide membrane of partial reduction in embodiment 1 detects figure, as seen from Figure 2, works as chlorination
When sodium water solution molar concentration >=1.5mol/L, there is diffraction maximum at (200) in diffraction curve.Fig. 3 is independently to prop up in embodiment 2
The XRD of the graphene oxide filter membrane of support detects figure, as seen from Figure 2, as sodium-chloride water solution molar concentration >=2.5mol/L
When, there is diffraction maximum at (200) in diffraction curve.XRD test result is shown soaks in the sodium-chloride water solution of respective concentration
The graphene oxide membrane of the graphene oxide film independently supported after bubble and partial reduction, inside there are XRD crystal diffraction peak,
(200) face of its main peak and corresponding sodium chloride salt crystal coincide, and shows to have formd significant crystal structure in film.
(2) synchronous wide-angle scatters WAXS (shanghai light source) test result
The WAXS test result of Fig. 4 shows that the graphene oxide membrane of the partial reduction in embodiment 1 is dense at different moles
There are crystal diffraction peak, main peak and (200) faces for corresponding to salt crystal to coincide for inside after impregnating in the NaCl aqueous solution of degree, table
Significant crystal structure is formd in bright film, which is consistent with the XRD testing result in (1)；In addition, being scattered from WAXS
Ring is it is known that crystal illustrates still to contain more moisture in film in two-dimensional orientation distribution in film；In Fig. 4, A is partial reduction
Graphene oxide membrane dry film, B are the NaCl crystal being precipitated in saturated solution, and C is the NaCl aqueous solution of 0.25mol/L (low concentration)
Wet film after immersion, D are the wet film after the NaCl aqueous solution soaking of 2.5mol/L (high concentration).
(3) salting liquid absorption result
Fig. 5 is the salinity in embodiment 2 in the salt water of graphene oxide membrane, the adsorbance of salinity and film, molten with salt
Liquid adsorbance characterizes ion enrichment degree.The graphene oxide membrane independently supported shows the absorption weighing result of NaCl aqueous solution
, after the NaCl aqueous solution soaking of different molar concentrations, the increment of salt water adsorption amount, film inner salt in film be increased,
It is found after conversion film forming inner salt water molar concentration, when 2.5mol/L (concentration of the saturated solution of 0.5 times of salt) concentration is impregnated,
Concentration has reached supersaturation in film, has reached the condition of crystallization.
It can be seen from above-mentioned test result at normal temperatures and pressures, the lower sodium-chloride water solution of concentration (1.0~
Crystallization 4.5mol/L) is precipitated in the presence of the graphene oxide membrane of the graphene oxide film and partial reduction that independently support.
Although specific embodiments of the present invention have been described above, it will be appreciated by those of skill in the art that this is only
For example, protection scope of the present invention is to be defined by the appended claims.Those skilled in the art without departing substantially from
Under the premise of the principle and substance of the present invention, many changes and modifications may be made, but these change and
Modification each falls within protection scope of the present invention.
Claims (10)
1. a kind of method of the unsaturation salting liquid crystallization based on carbon-based material, which is characterized in that it includes the following steps:
Carbon-based material is immersed in 10~120min in salting liquid, until precipitating crystal；
Wherein, the salting liquid is unsaturation solution, molar concentration >=1mol/L of the salting liquid.
2. the method as described in claim 1, which is characterized in that the carbon-based material is that the graphene oxide that independently supports is thin
Film, partial reduction graphene oxide membrane, with filter membrane support graphene oxide membrane or containing the carbon-based material of aromatic ring structure；
And/or the film of the carbon-based material with a thickness of 0.2 micron~100 microns, preferably 25 microns.
3. method according to claim 2, which is characterized in that the graphene oxide film independently supported uses method 1
It is prepared, the method 1 is the following steps are included: by graphene oxide solution drop coating in smooth hydrophobic paper surface, drying is
Obtain the graphene oxide membrane independently supported；
And/or the graphene oxide membrane with filter membrane support is prepared using method 2, the method 2 includes following step
It is rapid: graphene oxide solution to be filtered, filter membrane is drying to obtain the graphene oxide membrane with filter membrane support；Wherein, the suction filtration
It is filtered using filter membrane.
4. method as claimed in claim 3, which is characterized in that the preparation method packet of the graphene oxide membrane of the partial reduction
It includes the following steps: the graphene oxide membrane independently supported or the graphene oxide membrane with filter membrane support is subjected to water
Thermal response.
5. method as claimed in claim 3, which is characterized in that
In the method 1 or the method 2, the solvent of the graphene oxide solution is organic solvent or water, described organic molten
Agent is preferably one of ethyl alcohol, acetone and dimethyl sulfoxide or a variety of；
And/or the mass concentration of the graphene oxide solution is 0.1~10mg/mL, preferably 5mg/mL；
And/or in the method 2, the filter membrane is water phase filter membrane；
And/or in the method 1 or the method 2, the drying carries out in an oven；The temperature of the drying is 60~80
DEG C, preferably 70 DEG C；The time of the drying is 6~10 hours, preferably 8 hours；
And/or in the method 1 or the method 2, the hydro-thermal reaction carries out in deionized water；The hydro-thermal reaction
The dosage of deionized water is 20~50mL, preferably 30mL；The temperature of the hydro-thermal reaction is 160~200 DEG C, preferably
180℃。
6. the method as described in claim 1, which is characterized in that the salting liquid is potassium salt soln and/or sodium salt solution；It is described
Sodium salt is sodium sulphate, sodium carbonate, sodium fluoride, sodium chloride, sodium bromide or sodium iodide；The sylvite is potassium sulfate, potassium carbonate, fluorination
Potassium, potassium chloride, potassium bromide or potassium iodide；
And/or the salt in the salting liquid is calcium chloride, magnesium chloride or ammonium chloride.
7. the method as described in claim 1, which is characterized in that the salting liquid is inorganic salt solution or organic slat solution；Institute
The solvent for stating inorganic salt solution is water；The solvent of the organic slat solution is ethyl alcohol, methanol, acetone, glycerol, dichloroethanes, three
Vinyl chloride, chloroform or toluene.
8. the method as described in claim 1, which is characterized in that the molar concentration of the salting liquid is 2.5mol/L.
9. the method as described in claim 1, which is characterized in that the salting liquid is sodium-chloride water solution, the sodium chloride water
The molar concentration of solution is 1.0~4.5mol/L, preferably 2.0~4.0mol/L, is more preferably 2.5~3.0mol/L.
10. the method as described in claim 1, which is characterized in that the time of the immersion is 30min.
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| WO2016077867A1 (en) * | 2014-11-19 | 2016-05-26 | Monash University | Graphene oxide membranes and methods related thereto |
| CN106457159A (en) * | 2014-05-08 | 2017-02-22 | 洛克希德马丁公司 | Stacked two-dimensional materials and methods for producing structures incorporating same |
| CN106823830A (en) * | 2017-02-27 | 2017-06-13 | 中南大学 | A kind of preparation method of the self-supporting graphene oxide film with water phase stability high |
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2017
- 2017-09-13 CN CN201710822861.1A patent/CN109481950A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106457159A (en) * | 2014-05-08 | 2017-02-22 | 洛克希德马丁公司 | Stacked two-dimensional materials and methods for producing structures incorporating same |
| WO2016077867A1 (en) * | 2014-11-19 | 2016-05-26 | Monash University | Graphene oxide membranes and methods related thereto |
| CN104609410A (en) * | 2015-01-30 | 2015-05-13 | 浙江碳谷上希材料科技有限公司 | Preparation method of high-performance graphene porous membrane |
| CN106823830A (en) * | 2017-02-27 | 2017-06-13 | 中南大学 | A kind of preparation method of the self-supporting graphene oxide film with water phase stability high |
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