CN106731891A - A kind of carbonitride two-dimensional material composite membrane and its production and use - Google Patents
A kind of carbonitride two-dimensional material composite membrane and its production and use Download PDFInfo
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- CN106731891A CN106731891A CN201710106726.7A CN201710106726A CN106731891A CN 106731891 A CN106731891 A CN 106731891A CN 201710106726 A CN201710106726 A CN 201710106726A CN 106731891 A CN106731891 A CN 106731891A
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- nitridation carbon
- oxidation nitridation
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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
- B01D71/024—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/366—Apparatus therefor
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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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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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
- B01D69/12—Composite membranes; Ultra-thin membranes
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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
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
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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
- B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
Abstract
The invention discloses a kind of method for preparing oxidation nitridation carbon two-dimensional material composite membrane, comprise the following steps：1）Carbonitride is carried out into oxidation and obtains oxidation nitridation carbon, by the dispersion of oxidation nitridation carbon in a solvent, sheet is peeled off into by ultrasound, form oxidation nitridation carbon dispersion liquid；2）Oxidation nitridation carbon dispersion liquid and macromolecule filming liquid are mixed to form composite membrane film liquid；3）Carbonitride two-dimensional material composite membrane is formed in porous carrier surface by impregnation drying method.The method that the present invention prepares oxidation nitridation carbon two-dimensional material composite membrane can prepare thickness and can reconcile the composite membrane of high mechanical strength, for having good selection separating effect in gas separation field.
Description
Technical field
The present invention relates to a kind of technical field of chemical separation, and in particular to a kind of carbonitride two-dimensional material composite membrane and its system
Preparation Method.
Background technology
In chemical industry, often meet short chain low-boiling point alcohol and water forms the different azeotropic mixture of ratio, such as the alcohol of C2-C4
Class, as the isomer of ethanol, normal propyl alcohol, isopropanol and butanol, the efficient, separation of low energy consumption is a weight of people's research
One of point.Meanwhile, for H2, N2, CO2, CH4Separated Deng gas, synthesis gas prepares the separation of methyl alcohol in low-carbon alcohols, urea method is closed
Separation the recycling for methyl alcohol of methyl alcohol in the separation of methyl alcohol into dimethyl carbonate, and methyl alcohol oxidation generation dimethoxym ethane
And propulsion reaction is all had very great help to favourable direction.Industrial conventional separation method is variable-pressure rectification and extraction
Rectifying, but these methods have many defects, such as high energy consumption, apparatus expensive, need addition entrainer and complex operation etc..
Therefore, for Azeotrope separation finds a kind of efficient, cheap and easy separation method direction that always researcher makes great efforts.
In recent years, carbonitride two-dimensional material is more is applied to the fields such as photocatalysis, electro-catalysis.But it is a kind of similar stone
The two-dimensional material of black alkene, can be stripped into two-dimentional monolayer, and surface distributed the defect of pore size fixation, with outstanding person
The thermodynamics and chemical stability for going out.These properties are made it have as the potential quality of separation membrane.Carbonitride is led in UF membrane
Domain has broad application prospects, particularly in terms of Azeotrope separation finds a kind of efficient, cheap and easy separation method.
Correlative study needs to be enriched.
The content of the invention
The shortcoming of prior art in view of the above, it is an object of the invention to provide a kind of oxidation nitridation carbon two-dimensional material
Composite membrane and preparation method thereof, can reconcile the composite membrane of high mechanical strength, in gas separation field to obtain thickness.
To achieve these goals or other purposes, the present invention is achieved by the following technical solutions.
The invention discloses a kind of method for preparing oxidation nitridation carbon two-dimensional material composite membrane, comprise the following steps：
1) sheet by the dispersion of oxidation nitridation carbon in a solvent, is peeled off into by ultrasound, oxidation nitridation carbon dispersion liquid is formed；
2) oxidation nitridation carbon dispersion liquid and macromolecule filming liquid are mixed to form composite membrane film liquid；
3) carbonitride two-dimensional material composite membrane is formed in porous carrier surface by dipping-seasoning.
Preferably, step 1) in, oxidation nitridation carbon is to carry out oxidation processes acquisition using carbonitride.Specifically, step 1)
In, oxidation nitridation carbon is prepared using Hummers methods.Further, oxidation nitridation carbon is prepared including following using Hummers methods
Step：A) by the carbonitride addition concentrated sulfuric acid, potassium permanganate reaction is added；B) add water, and add aqueous hydrogen peroxide solution straight
Produced to there is no bubble, obtain dispersion liquid；C) dispersion liquid is carried out into separation of solid and liquid and obtains oxidation nitridation carbon.
It is highly preferred that during a) step of oxidation nitridation carbon is prepared using Hummers methods, the quality of carbonitride and potassium permanganate
Than being 1:(2~7).In step a), the mass volume ratio of carbonitride and the concentrated sulfuric acid is：1g/ (40~50) ml.In step a), instead
It is 1~4 hour between seasonable.In step b), the concentration of aqueous hydrogen peroxide solution is 25~35wt%.In step c), separation of solid and liquid
Also include cleaning step afterwards.
Preferably, step 1) in, in oxidation nitridation carbon dispersion liquid the mass-volume concentration of oxidation nitridation carbon be 0.3~
0.6mg/ml.It is highly preferred that step 1) in, the mass-volume concentration of oxidation nitridation carbon is 0.5mg/ in oxidation nitridation carbon dispersion liquid
ml。
Preferably, carbonitride is that high-temperature process acquisition is carried out to cdicynanmide, and the temperature of the high-temperature process is 500~600
℃。
Preferably, step 1) in solvent be selected from water, ethylene glycol and methyl alcohol in one or more.
Preferably, the macromolecule filming liquid is that polyvinyl alcohol or dimethyl silicone polymer dissolving are formed in a solvent.It is excellent
Selection of land, the solvent is selected from one or more in water, ethylene glycol, n-hexane and N-N- dimethylformamides.Preferably, it is high
The weight/mass percentage composition of polyvinyl alcohol is 0.1~5wt% in molecular film-forming liquid.Preferably, poly dimethyl in macromolecule filming liquid
The weight/mass percentage composition of siloxanes is 5~10wt%.
Preferably, the number-average molecular weight of the polyvinyl alcohol is 60000~80000.
Preferably, the number-average molecular weight of the dimethyl silicone polymer is 45000~65000.
Preferably, step 2) in, the mass ratio of oxidation nitridation carbon and polyvinyl alcohol or dimethyl silicone polymer for (1~
3):5.It is highly preferred that step 2) in, oxidation nitridation carbon is 2 with the mass ratio of polyvinyl alcohol or dimethyl silicone polymer:5.
Preferably, step 3) in, the porous carrier is selected from one or more in porous ceramics and porous stainless steel.
Preferably, step 3) in, the configuration of the porous carrier includes tubulose, sheet and hollow fiber.
Preferably, step 3) in, the dipping-seasoning is that porous carrier is put into composite membrane film liquid to be soaked every time
It is dried after stain.Preferably, dip time is 2~6min/ times.Preferably, dipping time is 1~10 time.Preferably, dry
Temperature is 20~80 DEG C.Preferably, drying time is 5~60min.
Preferably, processed before being carried out to porous carrier before the dipping, the pre-treatment is in 3- ammonia by the porous carrier
Soaked in propyl trimethoxy silicane solution.Preferably, the solvent in the 3- aminopropyl trimethoxysilanes solution is
Toluene or acetone.Preferably, in the 3- aminopropyl trimethoxysilanes solution, 3- aminopropyl trimethoxysilanes be 0.15~
0.35g/100ml。
Preferably, soaking temperature is 100~120 DEG C.Preferably, the soak time is at least 30min.
In order to reduce film forming defect, 60~180min of vacuum outgas is carried out to composite membrane film liquid.
A kind of oxidation nitridation carbon two-dimensional material composite membrane, is prepared by method described above.
Oxidation nitridation carbon two-dimensional material composite membrane as described above separates the purposes of water outlet in aqueous azeotrope.
Specifically, the organic phase of the aqueous azeotrope includes the alcohols of C2-C4, such as ethanol, propyl alcohol and its isomerism
Body, butanol and its isomer；Other organic mixed systems are the mixed solution of C1 and X, and wherein C1 is methyl alcohol, X including different
Propyl alcohol, dimethoxym ethane, dimethyl carbonate.
The method that the present invention prepares oxidation nitridation carbon two-dimensional material composite membrane can prepare thickness and can reconcile mechanical strength
Composite membrane high, for having good selection separating effect in gas separation field.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of carbonitride and oxidation nitridation carbon in embodiment 1.
Fig. 2 a are the x-ray photoelectron power spectrum Cls collection of illustrative plates of carbonitride in embodiment 1.
Fig. 2 b are the x-ray photoelectron power spectrum Cls collection of illustrative plates of oxidation nitridation carbon in embodiment 1.
Fig. 3 is carbonitride single dispersing projection electron microscope in embodiment 1.
Fig. 4 is oxidation nitridation carbon single dispersing projection electron microscope in embodiment 1.
Specific embodiment
Embodiments of the present invention are illustrated below by way of specific instantiation, those skilled in the art can be by this specification
Disclosed content understands other advantages of the invention and effect easily.The present invention can also be by specific realities different in addition
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
Before the specific embodiment of the invention is further described, it should be appreciated that protection scope of the present invention is not limited to down
State specific specific embodiment；It is also understood that the term used in the embodiment of the present invention is specific specific in order to describe
Embodiment, rather than in order to limit the scope of the invention.The test method of unreceipted actual conditions in the following example,
Generally according to normal condition, or according to the condition proposed by each manufacturer.
When embodiment provides number range, it should be appreciated that except non-invention is otherwise noted, two ends of each number range
Any one numerical value can select between point and two end points.Unless otherwise defined, in the present invention all technologies for using and
Scientific terminology is identical with the meaning that those skilled in the art of the present technique are generally understood that.Except the specific method, equipment used in embodiment,
Outside material, grasp and record of the invention according to those skilled in the art to prior art can also be used and this
Any method, equipment and material in the similar or equivalent prior art of method, equipment described in inventive embodiments, material come real
The existing present invention.
Oxidation nitridation carbon in the embodiment of the present invention is to be prepared using Hummers methods.Nitrogen oxide is prepared using Hummers methods
Change carbon to comprise the following steps：A) by the carbonitride addition concentrated sulfuric acid, potassium permanganate reaction is added；B) add water, and add peroxide
Change aqueous solution of hydrogen to be produced until there is no bubble, obtain dispersion liquid；C) dispersion liquid is carried out into separation of solid and liquid and obtains oxidation nitridation
Carbon.
It is highly preferred that during a) step of oxidation nitridation carbon is prepared using Hummers methods, the quality of carbonitride and potassium permanganate
Than being 1:(2~7).In step a), the mass volume ratio of carbonitride and the concentrated sulfuric acid is：1g/ (40~50) ml.In step a), instead
It is 1~4 hour between seasonable.In step b), the concentration of aqueous hydrogen peroxide solution is 25~35wt%.In step c), separation of solid and liquid
Also include cleaning step afterwards.
In the embodiment of the present invention：
Separation factor computing formula：α=(w2m/w2d)/(w1m/w1d).Wherein, w2mIt is the mass concentration of per-meate side water；w2d
It is the mass concentration of per-meate side ethanol；w1mIt is the mass concentration of feed water；w1dIt is the mass concentration of feed ethanol.
Permeation flux computing formula：J=Δs m/ (s × t), wherein, the product quality that Δ m is collected into for per-meate side, unit
It is kg；S is effective membrane area, and unit is m2；T is acquisition time, and unit is h.
Oxidation nitridation carbon is to be prepared via a method which to obtain in the embodiment of the present invention：
Oxidation processes are carried out by Hummers methods using carbonitride and prepares oxidation nitridation carbon.Carbonitride is that cdicynanmide is entered
Row high-temperature process is obtained, and the temperature of the high-temperature process is 500~600 DEG C.
In the embodiment of the present invention, aqueous azeotrope is separated using infiltration evaporation technique, the temperature of infiltration evaporation is 30~70
DEG C, osmotic lateral pressure is 1~300Pa, and feed rate is 10~500ml/min.
Embodiment 1
The present embodiment be prepared on tubular ceramic carrier oxidation nitridation carbon two-dimensional material-composite membrane of polyvinyl alcohol for point
From water and the mixture of C2-C4 alcohol.
It is as follows the step of hummer methods prepare oxidation nitridation carbon in the present embodiment.
The g-C of 1g3N4- 0825 powder, in the addition 50ml concentrated sulfuric acids.Under condition of ice bath, 3.5g potassium permanganate is slowly added to.
Flask is immersed in 35 DEG C of water-bath, is reacted 1 hour with magnetic stirrer.Then 200ml water is delayed under conditions of ice bath
Slowly it is added in flask, and adds 30% aqueous hydrogen peroxide solution to be produced until there is no bubble.The dispersion liquid for obtaining with from
Centrifugal separation, separates 1 hour by 10000 turns/min.The separator for obtaining is cleaned 3 times with deionized water, and pH reaches 7.50 DEG C afterwards
Lower vacuum drying 12h.Remember oxidation nitridation carbon.
Oxidation nitridation carbon two-dimensional material-composite membrane of polyvinyl alcohol specific method is prepared to comprise the following steps：
1) 10mg oxidation nitridation carbon is added in 20ml aqueous solvents, ultrasound makes its fully dispersed, forms 0.5mg/mL's
Oxidation nitridation carbon two-dimensional material suspension；
2) the 5wt% polyvinyl alcohol water solutions of the 0.5mg/mL oxidation nitridations carbon two-dimensional material suspension of 20mL and 0.514g
Mixing (oxidation nitridation carbon two-dimensional material:Polyvinyl alcohol=2:5) it is uniform, gained mixed liquor degassing 60min；
3) porous ceramic pipe is chosen as carrier, and the inside and outside footpath of porous ceramic pipe is respectively 10mm and 7mm, and inner surface is put down
Equal aperture 100nm, the end seal glaze of carrier two, effective film length 35mm；After cleaning drying 1h is calcined at 500 DEG C；Outer surface tetrafluoro
Band sealing；
4) carrier is dipped vertically into above-mentioned oxidation nitridation carbon two-dimensional material-polyvinyl alcohol hydrosol, is taken out after 2min,
10min is dried in 50 DEG C of vacuum drying ovens；12h is dried in 50 DEG C of vacuum drying ovens；Specifically, carrier is porous oxidation aluminum pipe；Dipping is carried
5000 μm/the s of decrease speed of daraf(reciprocal of farad), pull rate is 1000 μm/s, and dip time is 30s, and the residence time is 30s, dipping
Number is 1 time.
The aqueous azeotrope of C2-C4 alcohol is separated using infiltration evaporation separating technology, operation temperature is 30-70 DEG C, system pressure
Power is 0.1MPa, feedstock quality concentration XOH:H2O is 90:10.XOH is C2-C4 alcohol.
Embodiment 2
Oxidation nitridation carbon two-dimensional material-dimethyl silicone polymer composite membrane is prepared on tubular ceramic carrier for separation water
With the mixture of C2-C4 alcohol.
The step of preparing oxidation nitridation carbon with hummer methods in the present embodiment is as follows：The g-C of 1g3N4- 0825 powder, adds
The 40ml concentrated sulfuric acids.Under condition of ice bath, 3.5g potassium permanganate is slowly added to.Flask is immersed in 45 DEG C of water-bath, uses magnetic stirring apparatus
Stirring reaction 4 hours.Then under conditions of ice bath, 200ml water is slowly added into flask, and adds 30% peroxidating
Aqueous solution of hydrogen until there is no bubble to producing in flask.The dispersion liquid centrifugal separation for obtaining, separates 1 by 25000 turns/min
Hour.The separator for obtaining is cleaned 3 times with deionized water, and pH reaches 7.12h is vacuum dried at 50 DEG C afterwards.
The preparation method of oxidation nitridation carbon two-dimensional material-dimethyl silicone polymer composite membrane includes following step in the present embodiment
Suddenly：
Step 1：10mg oxidation nitridation carbon is added in 20ml alcohol solvents, ultrasound makes its fully dispersed；Formed
The oxidation nitridation carbon two-dimensional material suspension of 0.5mg/ml.
Step 2：The 0.5mg/mL oxidation nitridations carbon two-dimensional material alcohol suspension of 20mL and the 5% poly dimethyl silicon of 0.5g
Oxygen alkane/hexane solution mixing (oxidation nitridation carbon two-dimensional material:Dimethyl silicone polymer=2:5) uniform, gained mixed liquor takes off
Gas 60min.
Step 3：Porous ceramic pipe is chosen as carrier, the inside and outside footpath of porous ceramic pipe is respectively 10mm and 7mm, interior table
Face average pore size 100nm, the end seal glaze of carrier two, effective film length 35mm.After cleaning drying 1h is calcined at 500 DEG C.Use outer surface
Teflon tap is sealed.
Step 4：Carrier is dipped vertically into oxidation nitridation carbon two-dimensional material-polyvinyl alcohol hydrosol, is taken out after 2min,
10min is dried in 50 DEG C of vacuum drying ovens；12h is dried in 50 DEG C of vacuum drying ovens.5000 μm/the s of decrease speed of dip-coating method, lifting
Speed is 1000 μm/s, and dip time is 30s, and the residence time is 30s, and dipping time is 2 times.
The aqueous azeotrope of C2-C4 alcohol is separated using infiltration evaporation separating technology, operation temperature is 30-70 DEG C, system pressure
Power is 0.1MPa, feedstock quality concentration XOH:H2O is 90:10.XOH represents C2-C4 alcohol.
Embodiment 3
Oxidation nitridation carbon two-dimensional material self-assembled film is prepared on tubular ceramic carrier for the mixed of separation water and C2-C4 alcohol
Compound.
The step of preparing oxidation nitridation carbon with hummer methods in the present embodiment is as follows：The g-C of 1g3N4- 0825 powder, adds
The 45ml concentrated sulfuric acids.Under condition of ice bath, 3.5g potassium permanganate is slowly added to.Flask is immersed in 40 DEG C of water-bath, uses magnetic stirring apparatus
Stirring reaction 3 hours.Then under conditions of ice bath, 200ml water is slowly added into flask, and adds 30% peroxidating
Aqueous solution of hydrogen until there is no bubble to producing in flask.The dispersion liquid centrifugal separation for obtaining, separates 1 by 20000 turns/min
Hour.The separator for obtaining is cleaned 3 times with deionized water, and pH reaches 7.12h is vacuum dried at 50 DEG C afterwards.
The preparation method of oxidation nitridation carbon two dimension composite membrane is comprised the following steps in the present embodiment：
Step 1：10mg oxidation nitridation carbon is added in 20ml alcohol solvents, ultrasound makes its fully dispersed；Formed
The oxidation nitridation carbon two-dimensional material suspension of 0.5mg/ml.
Step 2：The 0.5mg/ml oxidation nitridations carbon two-dimensional material alcohol suspension of 20mL and the 5% poly dimethyl silicon of 0.5g
Oxygen alkane/hexane solution mixing (oxidation nitridation carbon two-dimensional material:Dimethyl silicone polymer=2:5) uniform, gained mixed liquor takes off
Gas 60min.
Step 3：Porous ceramic pipe is chosen as carrier, the inside and outside footpath of porous ceramic pipe is respectively 10mm and 7mm, interior table
Face average pore size 100nm, the end seal glaze of carrier two, effective film length 35mm；After cleaning drying 1h is calcined at 500 DEG C.Ceramic-film tube
Outer surface is covered with raw material band winding, is put into 100ml toluene, add 0.2g 3- aminopropyl trimethoxysilanes；At 110 DEG C
Lower heating stirring 1h, 12h is dried in 50 DEG C of vacuum drying ovens.
Step 4：Carrier is dipped vertically into above-mentioned oxidation nitridation carbon-polyvinyl alcohol hydrosol, is taken out after 2min, at 50 DEG C
10min is dried in vacuum drying oven；12h is dried in 50 DEG C of vacuum drying ovens.5000 μm/the s of decrease speed of dip-coating method, pull rate
It is 1000 μm/s, dip time is 30s, and the residence time is 30s, and dipping time is 2 times.
The aqueous azeotrope of C2-C4 alcohol is separated using infiltration evaporation separating technology, operation temperature is 30-70 DEG C, system pressure
Power is 0.1MPa, feedstock quality concentration XOH:H2O is 90:10.
Embodiment 4
Oxidation nitridation carbon two-dimensional material self-assembled film is prepared on flaky pottery carrier for the mixed of separation water and C2-C4 alcohol
Compound.
The step of preparing oxidation nitridation carbon with hummer methods in the present embodiment is as follows：The g-C of 1g3N4- 0825 powder, adds
The 40ml concentrated sulfuric acids.Under condition of ice bath, 3.5g potassium permanganate is slowly added to.Flask is immersed in 35 DEG C of water-bath, uses magnetic stirring apparatus
Stirring reaction 2 hours.Then under conditions of ice bath, 200ml water is slowly added into flask, and adds 30% peroxidating
Aqueous solution of hydrogen until there is no bubble to producing in flask.The dispersion liquid centrifugal separation for obtaining, separates 1 by 20000 turns/min
Hour.The separator for obtaining is cleaned 3 times with deionized water, and pH reaches 7.12h is vacuum dried at 50 DEG C afterwards.
The preparation method of oxidation nitridation carbon two dimension composite membrane is comprised the following steps in the present embodiment：
Step 1：10mg oxidation nitridation carbon is added in 20ml alcohol solvents, ultrasound makes its fully dispersed；Formed
The oxidation nitridation carbon two-dimensional material suspension of 0.5mg/ml.
Step 2：The 0.5mg/ml oxidation nitridations carbon two-dimensional material alcohol suspension of 20mL and the 5% poly dimethyl silicon of 0.5g
Oxygen alkane/hexane solution mixing (oxidation nitridation carbon two-dimensional material:Dimethyl silicone polymer=2:5) uniform, gained mixed liquor takes off
Gas 60min.
Step 3：Porous ceramics piece is chosen as carrier, 1h is calcined at 500 DEG C after cleaning drying.Ceramic diaphragm raw material band
Winding covering outer surface, is put into 100ml toluene, adds 0.25g 3- aminopropyl trimethoxysilanes；Heated at 100 DEG C and stirred
30min is mixed, 12h is dried in 50 DEG C of vacuum drying ovens.
Step 4：Carrier is immersed in above-mentioned oxidation nitridation carbon-polyvinyl alcohol hydrosol, is taken out after 2min, in 50 DEG C of vacuum
10min is dried in baking oven；12h is dried in 50 DEG C of vacuum drying ovens.5000 μm/the s of decrease speed of dip-coating method, pull rate is
1000 μm/s, dip time is 30s, and the residence time is 30s, and dipping time is 2 times.
The aqueous azeotrope of C2-C4 alcohol is separated using infiltration evaporation separating technology, operation temperature is 30-70 DEG C, system pressure
Power is 0.1MPa, feedstock quality concentration XOH:H2O is 90:10.
The separating effect of the oxidation nitridation carbon two-dimensional material composite membrane obtained in embodiment 1~4 is as shown in the table：Its Central Plains
Feed liquid water-alcohol mixture is water/ethanol, and ratio mass ratio is 1:9.
The above, only presently preferred embodiments of the present invention, it is not any to the present invention in form and substantial limitation,
It should be pointed out that for those skilled in the art, on the premise of the inventive method is not departed from, can also make
Some improvement and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations for developing, are Equivalent embodiments of the invention；Meanwhile, it is all according to substantial technological pair of the invention
The variation, modification and evolution of any equivalent variations that above-described embodiment is made, still fall within the scope of technical scheme
It is interior.
Claims (10)
1. a kind of method for preparing oxidation nitridation carbon two-dimensional material composite membrane, comprises the following steps：
1) carbonitride is carried out into oxidation and obtains oxidation nitridation carbon；By the dispersion of oxidation nitridation carbon in a solvent, peeled off into by ultrasound
Sheet, forms oxidation nitridation carbon dispersion liquid；
2) oxidation nitridation carbon dispersion liquid and macromolecule filming liquid are mixed to form composite membrane film liquid；
3) carbonitride two-dimensional material composite membrane is formed in porous carrier surface by dipping-seasoning.
2. method as claimed in claim 1, it is characterised in that step 1) in, prepare oxidation nitridation carbon and comprise the following steps：A) will
Carbonitride is added in the concentrated sulfuric acid, adds potassium permanganate reaction；B) add water, and add aqueous hydrogen peroxide solution until there is no gas
Bubble is produced, and obtains dispersion liquid；C) dispersion liquid is carried out into separation of solid and liquid and obtains oxidation nitridation carbon.
3. method as claimed in claim 1, it is characterised in that step 1) in, oxidation nitridation carbon in oxidation nitridation carbon dispersion liquid
Mass-volume concentration is 0.3~0.6mg/ml.
4. method as claimed in claim 2, it is characterised in that carbonitride is that high-temperature process acquisition, the height are carried out to cdicynanmide
The temperature of temperature treatment is 500~600 DEG C.
5. method as claimed in claim 1, it is characterised in that step 1) in solvent be selected from one kind in water, ethylene glycol and methyl alcohol
Or it is various.
6. method as claimed in claim 1, it is characterised in that the macromolecule filming liquid is polyvinyl alcohol or polydimethylsiloxanes
Alkane dissolving is formed in a solvent, the solvent be selected from the one kind in water, ethylene glycol, n-hexane and N-N- dimethylformamides or
It is various.
7. method as claimed in claim 6, it is characterised in that macromolecule filming liquid also includes the one kind or many in following characteristics
Kind：
The weight/mass percentage composition of polyvinyl alcohol is 0.1~5wt%；
The weight/mass percentage composition of dimethyl silicone polymer is 5~10wt% in macromolecule filming liquid；
The number-average molecular weight of the polyvinyl alcohol is 60000~80000；
The number-average molecular weight of the dimethyl silicone polymer is 45000~65000.
8. method as claimed in claim 1, it is characterised in that
Step 2) in, oxidation nitridation carbon is (1~3) with the mass ratio of polyvinyl alcohol or dimethyl silicone polymer:5；
Step 3) in, the porous carrier is selected from one or more in porous ceramics and porous stainless steel；
Step 3) in, the configuration of the porous carrier includes tubulose, sheet and hollow fiber；
Step 3) in, the dipping-seasoning be porous carrier is put into impregnated every time in composite membrane film liquid after done
It is dry.
9. a kind of oxidation nitridation carbon two-dimensional material composite membrane, is prepared by claim 1~8 any one methods described.
10. oxidation nitridation carbon two-dimensional material composite membrane separates water outlet in aqueous azeotrope as described in any one of claim 1~8
Purposes.
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| CN107441892A (en) * | 2017-07-25 | 2017-12-08 | 华南理工大学 | A kind of application of two-dimentional MXene films in gas separation |
| CN107983161A (en) * | 2017-11-23 | 2018-05-04 | 华南理工大学 | A kind of application of two dimension MXene films in water and separation of ethanol |
| CN107998904A (en) * | 2017-11-22 | 2018-05-08 | 华南理工大学 | One kind can be used for the separated g-C of gas3N4Two-dimensional nano piece film and preparation method thereof with separated in gas in application |
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| CN112897484A (en) * | 2021-01-14 | 2021-06-04 | 华南理工大学 | g-C without defect3N4Nanosheets, two-dimensional g-C3N4Nano sheet film, preparation method and application |
| CN114515519A (en) * | 2022-03-16 | 2022-05-20 | 南京工业大学 | Mixed matrix carbon molecular sieve membrane, preparation method and composite material prepared by using the same2H4/C2H6Use in separations |
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| CN114515519A (en) * | 2022-03-16 | 2022-05-20 | 南京工业大学 | Mixed matrix carbon molecular sieve membrane, preparation method and composite material prepared by using the same2H4/C2H6Use in separations |
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