CN104772043B - Sodium alginate-graphite phase carbon nitride nano-sheet hybridized composite membrane as well as preparation and application of composite membrane - Google Patents
Sodium alginate-graphite phase carbon nitride nano-sheet hybridized composite membrane as well as preparation and application of composite membrane Download PDFInfo
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Abstract
The invention relates to a sodium alginate-graphite phase carbon nitride nano-sheet hybridized composite membrane. The composite membrane is prepared by the steps of firstly, with melamine as the raw material, preparing ultrathin and porous graphite phase carbon nitride nano-sheet by using a hot separation and liquid-phase separation combined method; blending the nano-sheet and sodium alginate to obtain a casting membrane liquid; defoaming, then preparing the membrane by using a spin-coating method; performing cross-linking with a calcium chloride solution; and finally drying to obtain the sodium alginate-graphite phase carbon nitride nano-sheet hybridized composite membrane. According to the hybridized composite membrane, by virtue of the structure characteristic that the graphite phase carbon nitride nano-sheet is planar, ultrathin and porous, the thicknesses of separation layers are reduced; an orderly transmission channel is built; the transmission resistance of water molecule is lowered; the ethyl alcohol molecule is prevented from transmitting; therefore the osmosis and the selectivity of the membrane are improved simultaneously. According to the hybridized composite membrane, the preparation process is simple, raw materials are easily available and the structure is controllable, and the composite membrane is used for ethyl alcohol/water mixture separation, and has relative high osmosis flux and separation coefficient.
Description
Technical field
The present invention relates to a kind of UF membrane field, more particularly to a kind of sodium alginate-graphite phase carbon nitride nanometer sheet hydridization
Composite membrane and preparation and application.
Background technology
The energy and environment are the 21 century significant challenges that face of the whole world, and alcohol fuel is used as a kind of reproducible clean energy resource
Receive significant attention.Ethanol/water mixture is azeotropic system, and traditional rectificating method is difficult to efficiently separating between component,
Therefore fuel alcohol dewatering becomes the key technology of fuel ethanol production.As a kind of new separation technology, pervaporation technology
Realize separating using physics chemical action different between feed liquid each component and membrane material, do not limited by VLE, have
The advantages of easy to operate, environmental friendliness, energy consumption are low, product purity is high, for the separation of azeotropic system shows prominent advantage.
Membrane material is the core of pervaporation technology.To improve the application efficiency of process of pervaporation, membrane material should have high simultaneously
Permeability and selectivity.With macromolecule as continuous phase, macromolecular-inorganic hybrid membrane material of the inorganic filler as dispersion phase due to
Have the advantage of polymeric membrane and inoranic membrane concurrently, be expected to while obtain higher permeability and selectivity, become osmotic evaporation film field
Forward position.
Prepared by the design of hybridized film at present has following challenge：(1) preparation of small size filler.Membrane permeability and thickness
Degree has approximate inversely prroportional relationship, is the permeation flux for improving film, realizes the ultrathin of film, needs uniform, controllable preparing
Small size filler；(2) preparation of porous fillers.On the one hand, the porosity of filler is higher, and permeable molecule diffusion rate is got over
Hurry up, permeability of the membrane is higher.On the other hand, suitable pore size can hinder the larger molecule of kinetic diameter to pass through, and have
Sieve effect, improves the selectivity of film.
Graphite phase carbon nitride is a species graphite mould material, is formed by the monatomic lamella stacking that thickness is only 0.33nm,
Means can be peeled off etc. from, liquid phase by hot soarfing, obtain individual layer or which floor ultra-thin graphite phase carbon nitride nanometer sheet, be disclosure satisfy that
The demand of osmotic evaporation film ultrathin.There is the micropore of a large amount of size uniformities in graphite phase carbon nitride nanometer sheet, diameter is about
0.31nm, between hydrone (kinetic diameter is 0.26nm) and ethanol molecule (kinetic diameter is 0.45nm) size,
Hydrone can be allowed to pass freely through, while hindering the transmission of ethanol molecule.
The content of the invention
It is an object of the invention to provide a kind of sodium alginate-graphite phase carbon nitride nanometer sheet hybridization compounding film and prepare and
Using, using method of the hot soarfing from combining with liquid phase stripping, ultra-thin porous graphite phase carbon nitride nanometer sheet is prepared, pass through
The physical blending of sodium alginate and graphite phase carbon nitride nanometer sheet prepares hybridization film material, then be spun to support layer surface prepare it is miscellaneous
Change composite membrane.Using the superthin structure of graphite phase carbon nitride nanometer sheet, separating layer thickness can be effectively reduced, the infiltration for improving film is led to
Amount；Using the two-dimensional structure of graphite phase carbon nitride nanometer sheet, regular stratiform pattern can be formed in film, build orderly biography
Pass passage；Using the loose structure of graphite phase carbon nitride nanometer sheet, hydrone transmission resistance can be reduced, improve ethanol molecule and pass
Resistance is passed, while improving permeability of the membrane and selectivity.Hybridization compounding membrane material has following main feature：(1) by changing
Masking is filled a prescription, and can efficiently, neatly regulate and control membrane structure and physicochemical properties；(2) preparation process is simple, easily realizes the super of film
Thinning and large-scale production.It is contemplated that membrane material obtained in the method has stronger stability and anti-Swelling Capacity.By the party
Membrane material obtained in method is dehydrated for ethanol/water mixed system pervaporation, with higher permeation flux and separation factor.
A kind of sodium alginate-graphite phase carbon nitride nanometer sheet hybridization compounding film that the present invention is provided, is with the high score of porous
Used as supporting layer, sodium alginate-graphite phase carbon nitride nanometer sheet hybridized film is separating layer to sub- milipore filter；The macromolecule of the porous
Milipore filter is polyacrylonitrile ultrafiltration film, polysulphone super-filter membrane, Sulfonated Polysulfone UF Membranes, poly (ether-sulfone) ultrafiltration membrane and polyimides milipore filter
In one kind.The molecular cut off of the polymer ultrafiltration membrane of the porous is 100,000；Sodium alginate-the graphite phase carbon nitride is received
The thickness of rice piece hybridized film is about 500nm.The preparation process of the hybridization compounding film is as follows：
Step one, sodium alginate is added in deionized water and stirs 1-2h at 20-40 DEG C, be configured to mass concentration for 1-
2% sodium alginate soln；
Step 2, in the sodium alginate soln add graphite phase carbon nitride nanometer sheet, wherein, graphite phase carbon nitride is received
Rice piece consumption is the 1-5wt.% of sodium alginate, pours in container after stirring 3-6h at 20-40 DEG C, is stored at room temperature 0.5-1h and takes off
Bubble, obtains casting solution；
Step 3, the casting solution is spun to porous polymer ultrafiltration membrane surface, be dried 24-72h under room temperature, obtain
Obtain uncrosslinked sodium alginate-graphite phase carbon nitride nanometer sheet hybridization compounding film；
Step 4, by the uncrosslinked sodium alginate-graphite phase carbon nitride nanometer sheet hybridization compounding film immersion 0.5M's
In calcium chloride water, 5-20min is crosslinked under room temperature, then the calcium chloride solution of film surface residual is rinsed dry by deionized water
Only, 24-48h is dried under room temperature, sodium alginate-graphite phase carbon nitride nanometer sheet hybridization compounding film is obtained.
Further, the graphite phase carbon nitride nanometer sheet that step 2 is added is the concrete preparation with melamine as raw material
Process is：Melamine is placed in crucible, Muffle furnace roasting 3-5h at 500-600 DEG C, heating rate and cooling speed is put into
Rate is controlled in 2-5 DEG C/min, obtains yellow powder；After the yellow powder is ground, Muffle furnace roasting at 500 DEG C is put into
1-3h, heating rate and rate of temperature fall are controlled in 3-8 DEG C/min, obtain graphite phase carbon nitride powder；Under room temperature, by the stone
Black phase carbon nitride powder is distributed in ionized water, makes the dispersion liquid of 0.5-2mg/L, centrifugation after ultrasonically treated 6-12h, and 30
It is vacuum dried at DEG C, obtains graphite phase carbon nitride nanometer sheet.
Sodium alginate of the present invention-graphite phase carbon nitride nanometer sheet hybridization compounding film is used for into the separation of ethanol/water mixture,
Permeation flux is 1915-2602g/m2H, separation factor is 787-1653.
It is an advantage of the current invention that：Preparation process simplicity is controllable, and raw material is easy to get, mild condition.Obtained sodium alginate-stone
Black phase carbon nitride nanometer sheet hybridization compounding film, for the dehydration of ethanol/water mixture pervaporation, with higher separating property.
Description of the drawings
Fig. 1 is the sodium alginate-graphite phase carbon nitride nanometer sheet hybridization compounding film high power scanning electron obtained in embodiment 3
Microscope (SEM) cross-section photographs.
Fig. 2 is sodium alginate composite membrane high power SEM (SEM) cross-section photographs obtained in comparative example.
Specific embodiment
Specific description is done to the present invention below by case is embodied as.
A kind of sodium alginate proposed by the present invention-graphite phase carbon nitride nanometer sheet hybridization compounding film is with the macromolecule of porous
Used as supporting layer, sodium alginate-graphite phase carbon nitride nanometer sheet hybridized film is separating layer to milipore filter；The macromolecule of the porous surpasses
The molecular cut off of filter membrane is 100,000, the polymer ultrafiltration membrane of the porous can be polyacrylonitrile ultrafiltration film, polysulphone super-filter membrane,
One kind in Sulfonated Polysulfone UF Membranes, poly (ether-sulfone) ultrafiltration membrane and polyimides milipore filter；Sodium alginate-the graphite phase carbon nitride
The thickness of nanometer sheet hybridized film is about 500nm.
A kind of embodiment 1, sodium alginate-graphite phase carbon nitride nanometer sheet hybridization compounding film, its preparation process is as follows：
Step one, sodium alginate is added in deionized water and stirs 2h at 30 DEG C, be configured to the sea that mass concentration is 1.5%
Solution of sodium alginate, it is stand-by；
Step 2, with melamine as raw material, peel off the method that combines from liquid phase using hot soarfing, prepare graphite-phase nitrogen
Change carbon nanosheet：5g melamines are placed in crucible, Muffle furnace roasting 4h at 550 DEG C, heating rate and cooling speed is put into
Rate is controlled in 3 DEG C/min, obtains yellow powder；With mortar by yellow powder grinding after, be put into Muffle furnace at 500 DEG C
Roasting 2h, heating rate and rate of temperature fall are controlled in 5 DEG C/min, obtain graphite phase carbon nitride powder；Under room temperature, by the stone
Black phase carbon nitride powder is distributed in ionized water, makes the dispersion liquid of 1mg/L, and centrifugation after ultrasonically treated 6h is true at 30 DEG C
Sky is dried, and obtains graphite phase carbon nitride nanometer sheet；
Step 3, in sodium alginate soln obtained in step one add step 2 obtained in graphite phase carbon nitride nanometer
Piece, wherein, graphite phase carbon nitride nanometer sheet consumption is the 1wt.% of sodium alginate, pours in container after stirring 4h at 30 DEG C,
1h deaerations are stored at room temperature, sodium alginate-graphite phase carbon nitride nanometer sheet casting solution is obtained；
Step 4, by step 3 prepare casting solution be spun to porous polyacrylonitrile ultrafiltration film surface, under room temperature do
Dry 48h, obtains uncrosslinked sodium alginate-graphite phase carbon nitride nanometer sheet hybridization compounding film；
Step 5, the uncrosslinked sodium alginate for preparing step 4-graphite phase carbon nitride nanometer sheet hybridization compounding film leaching
In entering the calcium chloride water of 0.5M, 10min is crosslinked under room temperature, then deionized water is by the calcium chloride solution of film surface residual
Rinse well, 24h is dried under room temperature, obtain sodium alginate-graphite phase carbon nitride nanometer sheet hybridization compounding film.
The sodium alginate prepared with embodiment 1-graphite phase carbon nitride nanometer sheet hybridization compounding film carries out ethanol/water point
From performance test.Using membrane separation plant, at 76 DEG C, ethanol/water mass ratio is 9 in material liquid:Carry out under conditions of 1 ethanol/
Water separable performance can be tested, and permeation flux is 1915g/m2H, separation factor is 787.
A kind of embodiment 2, sodium alginate-graphite phase carbon nitride nanometer sheet hybridization compounding film, its preparation process and embodiment 1
It is essentially identical, it is different only in that, in step 3, graphite phase carbon nitride nanometer sheet consumption is changed to by the 1wt.% for accounting for sodium alginate
Account for the 2wt.% of sodium alginate.
The sodium alginate prepared with embodiment 2-graphite phase carbon nitride nanometer sheet hybridization compounding film carries out ethanol/water point
From performance test.Using membrane separation plant, at 76 DEG C, ethanol/water mass ratio is 9 in material liquid:Carry out under conditions of 1 ethanol/
Water separable performance can be tested, and permeation flux is 2232g/m2H, separation factor is 1254.
A kind of embodiment 3, sodium alginate-graphite phase carbon nitride nanometer sheet hybridization compounding film, its preparation process and embodiment 1
It is essentially identical, it is different only in that, in step 3, graphite phase carbon nitride nanometer sheet consumption is changed to by the 1wt.% for accounting for sodium alginate
Account for the 3wt.% of sodium alginate.High power SEM of the sodium alginate for finally giving-graphite phase carbon nitride nanometer sheet hybridization compounding film is broken
Face photo is as shown in Figure 1.
The sodium alginate prepared with embodiment 3-graphite phase carbon nitride nanometer sheet hybridization compounding film carries out ethanol/water point
From performance test.Using membrane separation plant, at 76 DEG C, ethanol/water mass ratio is 9 in material liquid:Carry out under conditions of 1 ethanol/
Water separable performance can be tested, and permeation flux is 2469g/m2H, separation factor is 1653.
A kind of embodiment 4, sodium alginate-graphite phase carbon nitride nanometer sheet hybridization compounding film, its preparation process and embodiment 1
It is essentially identical, it is different only in that, in step 3, graphite phase carbon nitride nanometer sheet consumption is changed to by the 1wt.% for accounting for sodium alginate
Account for the 4wt.% of sodium alginate.
The sodium alginate prepared with embodiment 4-graphite phase carbon nitride nanometer sheet hybridization compounding film carries out ethanol/water point
From performance test.Using membrane separation plant, at 76 DEG C, ethanol/water mass ratio is 9 in material liquid:Carry out under conditions of 1 ethanol/
Water separable performance can be tested, and permeation flux is 2250g/m2H, separation factor is 1331.
A kind of comparative example, sodium alginate hybridization compounding film, its preparation process is as follows：
Step one, sodium alginate is added in deionized water and stirs 2h at 30 DEG C, be configured to the sea that concentration is 1.5wt.%
Solution of sodium alginate.Then proceed to be poured in container after stirring 4h at 30 DEG C, be stored at room temperature 1h deaerations, obtain sodium alginate casting film
Liquid；
Step 2, casting solution prepared by step one is spun to porous polyacrylonitrile ultrafiltration film surface, under room temperature do
Dry 48h, obtains uncrosslinked sodium alginate composite membrane；
In step 3, the calcium chloride water of the uncrosslinked sodium alginate composite membrane immersion 0.5M for preparing step 2,
10min is crosslinked under room temperature, then deionized water rinses well the calcium chloride solution of film surface residual, under room temperature 24h is dried,
Obtain sodium alginate hybridization compounding film.The high power SEM cross-section photographs of the sodium alginate composite membrane for finally giving are as shown in Figure 2.
The sodium alginate composite membrane prepared with comparative example carries out ethanol/water separating property test.Set using UF membrane
Standby, at 76 DEG C, ethanol/water mass ratio is 9 in material liquid:Ethanol/water separating property test, permeation flux are carried out under conditions of 1
For 1544g/m2H, separation factor is 511.
To sum up, the present invention controllable, the raw material for preparing sodium alginate-graphite phase carbon nitride nanometer sheet hybridization compounding membrane process simplicity
It is easy to get, mild condition, obtained sodium alginate-graphite phase carbon nitride nanometer sheet hybridization compounding film oozes for ethanol/water mixture
Saturating dehydration by evaporation, with higher separating property.Sodium alginate-graphite phase carbon nitride nanometer sheet the hydridization prepared in embodiment 3
Compound film properties are optimal, and flux improves 59.9% compared with sodium alginate composite membrane in comparative example, and separation factor improves
223.5%.
Although above in conjunction with figure, invention has been described, the invention is not limited in above-mentioned specific embodiment party
Formula, above-mentioned specific embodiment is only schematic, rather than restricted, and one of ordinary skill in the art is at this
Under bright enlightenment, without deviating from the spirit of the invention, many variations can also be made, these belong to the guarantor of the present invention
Within shield.
Claims (4)
1. the preparation method of a kind of sodium alginate-graphite phase carbon nitride nanometer sheet hybridization compounding film, the hybridization compounding film is with many
Used as supporting layer, sodium alginate-graphite phase carbon nitride nanometer sheet hybridized film is separating layer to the polymer ultrafiltration membrane in hole；The porous
Polymer ultrafiltration membrane molecular cut off be 100,000；The thickness of the sodium alginate-graphite phase carbon nitride nanometer sheet hybridized film
For 500nm；It is characterized in that：The hybridization compounding film is prepared according to the following steps：
Step one, sodium alginate is added in deionized water and stirs 1-2h at 20-40 DEG C, be configured to mass concentration for 1-2%'s
Sodium alginate soln；
Step 2, in the sodium alginate soln add graphite phase carbon nitride nanometer sheet, wherein, graphite phase carbon nitride nanometer sheet
Consumption is the 1-5wt.% of sodium alginate, pours in container after stirring 3-6h at 20-40 DEG C, is stored at room temperature 0.5-1h deaerations,
Obtain casting solution；
Step 3, the casting solution is spun to porous polymer ultrafiltration membrane surface, be dried 24-72h under room temperature, obtain not
The sodium alginate of crosslinking-graphite phase carbon nitride nanometer sheet hybridization compounding film；
Step 4, the chlorination that the uncrosslinked sodium alginate-graphite phase carbon nitride nanometer sheet hybridization compounding film is immersed 0.5M
In the calcium aqueous solution, 5-20min is crosslinked under room temperature, then deionized water rinses well the calcium chloride solution of film surface residual,
24-48h is dried under room temperature, sodium alginate-graphite phase carbon nitride nanometer sheet hybridization compounding film is obtained.
2. the preparation method of sodium alginate-graphite phase carbon nitride nanometer sheet hybridization compounding film according to claim 1, its feature
It is：The polymer ultrafiltration membrane of the porous is polyacrylonitrile ultrafiltration film, polysulphone super-filter membrane, Sulfonated Polysulfone UF Membranes, polyether sulfone
One kind in milipore filter and polyimides milipore filter.
3. the preparation method of sodium alginate-graphite phase carbon nitride nanometer sheet hybridization compounding film according to claim 1, wherein,
The graphite phase carbon nitride nanometer sheet that step 2 is added is, with melamine as raw material, to prepare as steps described below：
Step one, melamine is placed in crucible, is put into Muffle furnace roasting 3-5h, heating rate and drop at 500-600 DEG C
Warm speed is controlled in 2-5 DEG C/min, obtains yellow powder；
Step 2, the yellow powder is ground after, be put into Muffle furnace roasting 1-3h at 500 DEG C, heating rate and cooling speed
Rate is controlled in 3-8 DEG C/min, obtains graphite phase carbon nitride powder；
Under step 3, room temperature, the graphite phase carbon nitride powder is distributed in ionized water, makes the dispersion liquid of 0.5-2mg/L,
Centrifugation after ultrasonically treated 6-12h, is vacuum dried at 30 DEG C, obtains graphite phase carbon nitride nanometer sheet.
4. prepared by a kind of preparation method of sodium alginate as claimed in claim 1-graphite phase carbon nitride nanometer sheet hybridization compounding film
The sodium alginate for obtaining-graphite phase carbon nitride nanometer sheet hybridization compounding film answering in the dehydration of ethanol/water mixture pervaporation
With.
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