CN106474939A - A kind of modified carbon nano-tube/graphene oxide shitosan is combined poly (ether-sulfone) ultrafiltration membrane and its preparation method and application - Google Patents
A kind of modified carbon nano-tube/graphene oxide shitosan is combined poly (ether-sulfone) ultrafiltration membrane and its preparation method and application Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
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Abstract
The invention discloses a kind of modified carbon nano-tube/graphene oxide shitosan is combined poly (ether-sulfone) ultrafiltration membrane and its preparation method and application, described modified carbon nano-tube/graphene oxide shitosan is combined poly (ether-sulfone) ultrafiltration membrane and is mainly using polyether sulfone as supporting layer, and CNT or graphene oxide and shitosan are made up of packed layer.With respect to prior art, the present invention by carbon nano-tube modification or utilizes graphene oxide, is combined polyether sulfone in conjunction with shitosan and obtains a kind of new ultrafilter membrane, substantially increases the performance of film.Good to the removal effect of mushroom and Microcystin, can carry out at normal temperatures, low cost and preparation method are simple, implementation is strong, can conscientiously improve household drinking water safety guarantee.
Description
Technical field
The invention discloses a kind of modified carbon nano-tube/graphene oxide-shitosan is combined poly (ether-sulfone) ultrafiltration membrane and its system
Preparation Method and application, belong to ultrafiltration membrane technique field.
Background technology
Water transfer pipe network system in city is a very huge and complicated construction project, in water from water factory to user
During need to transport for a long time, therefore, urban drinking water transmission during can in water transfer pipe network the time of staying longer, impact
The quality of municipal drinking water.Additionally, the service life of city water transfer pipe network is generally longer at this stage, or even there is showing of corrosion and ageing
As affecting safely to urban drinking water.Wherein, the stability of Algae toxins is very strong, and conventional water treatment technology is not
It effectively can be removed, and Algae toxins can damage to human body in extremely low concentration, and body eutrophication becomes tight
Weight, leads to self-purification of water function slump of disastrous proportions.Therefore, Algae toxins pollution problem all becomes in China and other countries in the world
For one of more prominent water environmental problems.Additionally, the pollution of microorganism also allows of no optimist in drinking water.
At present, the common process of Microcystin mainly includes prechlorination, UV, ozonisation, activated carbon adsorption and film
Filter technology etc. but ultrafilter membrane is rarely reported at home to the removal efficiency of Microcystin and the research of mechanism, prior art
Have and using ultrafilter membrane, microorganism mushroom in drinking water and Microcystin are removed, but still suffer from some problems, such as
General ultrafiltration membrane process can not be stablized and effectively to remove Microcystin (MC-RR, MC-LR), and clearance is over time
Prolongation is gradually lowered, and it is also affected by membrane flux to the clearance of Microcystin, and the membrane flux of general ultrafilter membrane compares
Little, the adsorbance on film surface for the Microcystin and the rate of adsorption are all than relatively low.Additionally, being modified to ultrafilter membrane in the past leading
Syllabus be provided to remove water body in other common pollutant, be not directed to microcystin in drinking water and microorganism
Pollution problem, although and the removal efficiency of pollutant is highly improved, modified relatively costly, examine in terms of economic benefit
Worry is unworthy.
Content of the invention
Goal of the invention：For above-mentioned technical problem, the invention provides a kind of modified carbon nano-tube/graphene oxide-shell
Polysaccharide is combined poly (ether-sulfone) ultrafiltration membrane and preparation method and application.
Technical scheme：To achieve the above object of the invention, the invention provides a kind of modified carbon nano-tube/graphene oxide-
Shitosan is combined poly (ether-sulfone) ultrafiltration membrane, and it is mainly using polyether sulfone as supporting layer, and CNT or graphene oxide and shell gather
Sugar is made up of packed layer.
Present invention also offers described modified carbon nano-tube/graphene oxide-shitosan is combined the system of poly (ether-sulfone) ultrafiltration membrane
Preparation Method, comprises the following steps：
(1) basement membrane solution is prepared：Polyethersulfone resin is dissolved in organic solvent, adds inorganic substances additive and organic
Material additive, stirring obtains basement membrane solution；
(2) carbon nano-tube modification：Original CNT CNTs adds supersound process in concentrated acid mixed solution, uses deionization
It is washed to neutrality, vacuum drying, obtain modified carbon nano-tube；
(3) graphene oxide solution：Graphene oxide is added in organic solvent, supersound process, forms graphene oxide
Solution；
(4) chitosan solution is prepared:Shitosan is dissolved in deionized water, separately adds salpeter solution, obtains chitosan solution；
(5) casting solution is prepared：Chitosan solution and modified carbon nano-tube or graphene oxide solution are added to basement membrane molten
In liquid, separately add glutaraldehyde solution, after stirring, standing a period of time, carries out deaeration process to reactant liquor, obtain casting solution；
(6) film：Under uniform temperature and damp condition, casting solution is poured on the plate of cleaning, carries out film；
(7) film forming：Under the conditions of uniform temperature, the above-mentioned plate level scribbling casting solution is immersed in organic solution, treats film
After disengaging, deionized water is soaked, and aseptic drying obtains final product.
Preferably, in described step (1), organic solvent is one of N-N- dimethyl acetylamide, N-N- dimethylformamide
Or two kinds；Inorganic substances additive is anhydrous Lithium chloride, anhydrous sodium chloride, anhydrous potassium chloride, anhydrous sodium sulfate and anhydrous sulfur
One or more of sour potassium；Organic substance additive be one of ethanol, Polyvinylpyrrolidone, isopropanol, acetone or
Multiple.
Preferably, in described step (1), with weight ratio meter, polyethersulfone resin：Organic solvent：Inorganic substances additive：Organic
Material additive=(5-8)：(20-30)：(0.2-0.5)：(2.5-4.0).
Preferably, in described step (2), concentrated acid mixed solution is acetic acid, dense H2SO4With dense HNO3Mixed acid, wherein acetic acid,
Dense H2SO4With dense HNO3Volume range be (2-3)：(2-5)：(0.5-1.5).
Preferably, in described step (3), organic solvent is one of N-N- dimethyl acetylamide, N-N- dimethylformamide
Or two kinds.
Preferably, in described step (3), the concentration range of graphene oxide solution is 0.1%-3% (g/100ml).
Preferably, in described step (4), the concentration range of chitosan solution is 0.5%-1.0% (g/100ml).
Preferably, in described step (5), the addition ratio of each component is：Chitosan solution：Modified carbon nano-tube/graphene oxide
Solution：Basement membrane solution=(15-25)：(0.3-0.5)/(15-25)：(60-80)(ml：g/ml：ml).
Preferably, in described step (6), temperature is 20-28 DEG C, and humidity is 35%-45%.
Preferably, in described step (7), temperature is 13-20 DEG C, and organic solution is the N-N- bis- of 10%-15% (g/100ml)
Methyl vinyl amine aqueous solution.
The amount of salpeter solution and the middle amount adding glutaraldehyde solution of step (5) is added to be on a small quantity, because step in step (4)
Suddenly need sour environment during shitosan dissolving in (4), therefore add a small amount of salpeter solution, shitosan can be made to dissolve, nitric acid
The addition of solution and concentration do not produce substantial effect to the present invention；Glutaraldehyde solution is added to be in order to solid in step (5)
The fixed new Modified Membrane being formed, its addition and concentration do not produce substantial effect to the present invention.
The present invention finally additionally provides described modified carbon nano-tube/graphene oxide-shitosan and is combined poly (ether-sulfone) ultrafiltration membrane
For the removal to microorganism mushroom and Microcystin in household drinking water.
Technique effect：With respect to prior art, the present invention by carbon nano-tube modification or utilizes graphene oxide, in conjunction with shell
Polysaccharide is combined polyether sulfone and obtains a kind of new ultrafilter membrane, substantially increases the performance of film.Removal to mushroom and Microcystin
Effect is good, can carry out at normal temperatures, and low cost and preparation method are simple, and implementation is strong, can conscientiously improve household drinking water peace
All risk insurance hinders.
Specific embodiment
Further describe technical solution of the present invention with reference to specific embodiment：
Wherein, MC-RR and MC-LR is one kind of Microcystin MCs.
Embodiment 1
(1) basement membrane solution is prepared
5g polyethersulfone resin (PES) is added in the beaker A filling 25gN-N- dimethylacetamide solvent, adds
0.2g anhydrous Lithium chloride and 2.5g Polyvinylpyrrolidone, are stirred at room temperature, and form basement membrane solution.
(2) carbon nano-tube modification
Improve dispersibility in water for the CNT CNTs using acid oxidation, CNTs that will be original is at a temperature of 70 DEG C
It is placed in the mixed solution (2 of acetic acid, concentrated sulphuric acid and concentrated nitric acid:2:1) utilize supersound process 5h in, deionized water is rinsed to neutrality
It is positioned over after vacuum drying in beaker B.
(3) chitosan solution is prepared
Weigh 2.5g shitosan, add deionized water to be dissolved in beaker C, separately add 5mL (1+5) (nitric acid and deionized water
Volume ratio is 1:Salpeter solution 5, below in the same manner), constant volume in 500mL volumetric flask D, obtain chitosan solution.
(4) casting solution is prepared
The modified CNT of 0.3g in chitosan solution 15mL in volumetric flask D and beaker B is added to basement membrane in beaker A
In solution, separately add a small amount of glutaraldehyde solution, stir 6h, stand a few houres, deaeration process is carried out to reactant liquor, obtains casting film
Liquid, stand-by.
(5) film
Under 20 DEG C and 35% damp condition, casting solution in (4) is poured on the glass plate of cleaning, carries out film.
(6) film forming
And then step (5), under the conditions of 13 DEG C, the glass plate level scribbling casting solution are immersed 10%N-N- dimethyl
In acetyl amine aqueous solution, after film departs from, deionized water soaks 2d, is placed in 60 DEG C of sterilizing ovens and 8h is dried, and preserves stand-by.
Take certain water factory's water outlet to be test water, processed with institute's masking, after 1d, effect is as follows：
| Before processing concentration | Concentration after process | Clearance | |
| Total plate count | 200CFU/mL | 25CFU/mL | 87.5% |
| MC-RR | 1.5ug/L | 0.40ug/L | 73.3% |
| MC-LR | 1.8ug/L | 0.55ug/L | 69.4% |
Embodiment 2
(1) basement membrane solution is prepared
5g polyethersulfone resin (PES) is added in the beaker A filling 30gN-N- solvent dimethylformamide, adds
0.4g anhydrous sodium chloride and 2.5g ethanol, are stirred at room temperature, and form basement membrane solution.
(2) carbon nano-tube modification
Improve dispersibility in water for the CNT CNTs using acid oxidation, CNTs that will be original is at a temperature of 70 DEG C
It is placed in the mixed solution (3 of acetic acid, concentrated sulphuric acid and concentrated nitric acid:5:1.5) in utilize supersound process 5h, deionized water rinse in
Property vacuum drying after be positioned in beaker B.
(3) chitosan solution is prepared
Weigh 3.0g shitosan, add deionized water to be dissolved in beaker C, separately add 5mL (1+10) salpeter solution, in
Constant volume in 500mL volumetric flask D, obtains chitosan solution.
(4) casting solution is prepared
The modified CNT of 0.35g in chitosan solution 15mL in volumetric flask D and beaker B is added to base in beaker A
In coating solution, separately add a small amount of glutaraldehyde solution, stir 6h, stand a few houres, deaeration process is carried out to reactant liquor, obtains casting film
Liquid, stand-by.
(5) film
Under 22 DEG C and 40% damp condition, casting solution in (4) is poured on the glass plate of cleaning, carries out film.
(6) film forming
And then step (5), under the conditions of 20 DEG C, the glass plate level scribbling casting solution are immersed 11%N-N- dimethyl
In acetyl amine aqueous solution, after film departs from, deionized water soaks 2d, is placed in 60 DEG C of sterilizing ovens and 8h is dried, and preserves stand-by.
Take certain water factory's water outlet to be test water, processed with institute's masking, after 1d, effect is as follows：
| Before processing concentration | Concentration after process | Clearance | |
| Total plate count | 200CFU/mL | 20CFU/mL | 90.0% |
| MC-RR | 1.5ug/L | 0.30ug/L | 80.0% |
| MC-LR | 1.8ug/L | 0.50ug/L | 72.2% |
Embodiment 3
(1) basement membrane solution is prepared
8g polyethersulfone resin (PES) is added in the beaker A filling 30gN-N- dimethylacetamide solvent, adds
0.5g anhydrous potassium chloride and 4.0g isopropanol, are stirred at room temperature, and form basement membrane solution.
(2) carbon nano-tube modification
Improve dispersibility in water for the CNT CNTs using acid oxidation, CNTs that will be original is at a temperature of 80 DEG C
It is placed in the mixed solution (2 of acetic acid, concentrated sulphuric acid and concentrated nitric acid:3:0.5) in utilize supersound process 7h, deionized water rinse in
Property vacuum drying after be positioned in beaker B.
(3) chitosan solution is prepared
Weigh a certain amount of 3.0g shitosan, add deionized water to be dissolved in beaker C, separately add 10mL (1+10) nitric acid molten
Liquid, constant volume in 500mL volumetric flask D, obtain chitosan solution.
(4) casting solution is prepared
The modified CNT of 0.5g in chitosan solution 20mL in volumetric flask D and beaker B is added to basement membrane in beaker A
In solution, separately add a small amount of glutaraldehyde solution, stir 5h, stand a few houres, deaeration process is carried out to reactant liquor, obtains casting film
Liquid, stand-by.
(5) film
Under 24 DEG C and 40% damp condition, casting solution in (4) is poured on the glass plate of cleaning, carries out film.
(6) film forming
And then step (5), under the conditions of 18 DEG C, the glass plate level scribbling casting solution are immersed 15%N-N- dimethyl
In acetyl amine aqueous solution, after film departs from, deionized water soaks 2d, is placed in 60 DEG C of sterilizing ovens and 8h is dried, and preserves stand-by.
Take certain water factory's water outlet to be test water, processed with institute's masking, after 1d, effect is as follows：
| Before processing concentration | Concentration after process | Clearance | |
| Total plate count | 200CFU/mL | 25CFU/mL | 87.5% |
| MC-RR | 1.5ug/L | 0.32ug/L | 78.7% |
| MC-LR | 1.8ug/L | 0.54ug/L | 70.0% |
Embodiment 4
(1) basement membrane solution is prepared
6g polyethersulfone resin (PES) is added in the beaker A filling 25gN-N- solvent dimethylformamide, adds
0.3g anhydrous sodium sulfate and 3.0g acetone, are stirred at room temperature, and form basement membrane solution.
(2) carbon nano-tube modification
Improve dispersibility in water for the CNT CNTs using acid oxidation, CNTs that will be original is at a temperature of 75 DEG C
It is placed in the mixed solution (2 of acetic acid, concentrated sulphuric acid and concentrated nitric acid:3:1) utilize supersound process 7h in, deionized water is rinsed to neutrality
It is positioned over after vacuum drying in beaker B.
(3) chitosan solution is prepared
Weigh a certain amount of 3.5g shitosan, add deionized water to be dissolved in beaker C, separately add 5mL (1+10) salpeter solution,
Constant volume in 500mL volumetric flask D, obtains chitosan solution.
(4) casting solution is prepared
Modified CNT 0.45g in chitosan solution 20mL in volumetric flask D and beaker B is added to base in beaker A
In coating solution, separately add a small amount of glutaraldehyde solution, stir 4h, stand a few houres, deaeration process is carried out to reactant liquor, obtains casting film
Liquid, stand-by.
(5) film
Under 28 DEG C and 42% damp condition, casting solution in (4) is poured on the glass plate of cleaning, carries out film.
(6) film forming
And then step (5), under the conditions of 20 DEG C, the glass plate level scribbling casting solution are immersed 12%N-N- dimethyl
In acetyl amine aqueous solution, after film departs from, deionized water soaks 2d, is placed in 60 DEG C of sterilizing ovens and 8h is dried, and preserves stand-by.
Take certain water factory's water outlet to be test water, processed with institute's masking, after 1d, effect is as follows：
| Before processing concentration | Concentration after process | Clearance | |
| Total plate count | 200CFU/mL | 12CFU/mL | 94.0% |
| MC-RR | 1.5ug/L | 0.28ug/L | 81.3% |
| MC-LR | 1.8ug/L | 0.49ug/L | 72.8% |
Embodiment 5
(1) basement membrane solution is prepared
5g polyethersulfone resin (PES) is added in the beaker A filling 30gN-N- dimethylacetamide solvent, adds
0.5g anhydrous potassium sulfate and 4.0g Polyvinylpyrrolidone, are stirred at room temperature, and form basement membrane solution.
(2) graphene oxide solution is prepared
A certain amount of graphene oxide is added in N-N- dimethyl acetylamide, supersound process, forms graphene oxide molten
Liquid, is placed in beaker B, and concentration is 0.1%.
(3) chitosan solution is prepared
Weigh a certain amount of 4.0 shitosans, add deionized water to be dissolved in beaker C, separately add 10mL (1+10) salpeter solution,
Constant volume in 500mL volumetric flask D, obtains chitosan solution.
(4) casting solution is prepared
Graphene oxide solution 15ml in chitosan solution 20mL and beaker B in volumetric flask D is added to base in beaker A
In coating solution, separately add a small amount of glutaraldehyde solution, stir 6h, stand a few houres, deaeration process is carried out to reactant liquor, obtains casting film
Liquid, stand-by.
(5) film
Under 26 DEG C and 45% damp condition, casting solution in (4) is poured on the glass plate of cleaning, carries out film.
(6) film forming
And then step (5), under the conditions of 15 DEG C, the glass plate level scribbling casting solution are immersed 14%N-N- dimethyl
In acetyl amine aqueous solution, after film departs from, deionized water soaks 2d, is placed in 60 DEG C of sterilizing ovens and 8h is dried, and preserves stand-by.
Take certain water factory's water outlet to be test water, processed with institute's masking, after 1d, effect is as follows：
| Before processing concentration | Concentration after process | Clearance | |
| Total plate count | 200CFU/mL | 18CFU/mL | 91.0% |
| MC-RR | 1.5ug/L | 0.31ug/L | 79.3% |
| MC-LR | 1.8ug/L | 0.51ug/L | 71.7% |
Embodiment 6
(1) basement membrane solution is prepared
8g polyethersulfone resin (PES) is added in the beaker A filling 20gN-N- solvent dimethylformamide, adds
0.4g anhydrous Lithium chloride and 3.5g Polyvinylpyrrolidone, are stirred at room temperature, and form basement membrane solution.
(2) graphene oxide solution is prepared
A certain amount of graphene oxide is added in N-N- dimethylformamide, supersound process, forms graphene oxide molten
Liquid, is placed in beaker B, and concentration is 1.5%.
(3) chitosan solution is prepared
Weigh a certain amount of 4.5g shitosan, add deionized water to be dissolved in beaker C, separately add 10mL (1+5) salpeter solution,
Constant volume in 500mL volumetric flask D, obtains chitosan solution.
(4) casting solution is prepared
Graphene oxide solution 25ml in chitosan solution 25mL and beaker B in volumetric flask D is added to base in beaker A
In coating solution, separately add a small amount of glutaraldehyde solution, stir 6h, stand a few houres, deaeration process is carried out to reactant liquor, obtains casting film
Liquid, stand-by.
(5) film
Under 28 DEG C and 38% damp condition, casting solution in (4) is poured on the glass plate of cleaning, carries out film.
(6) film forming
And then step (5), under the conditions of 17 DEG C, the glass plate level scribbling casting solution are immersed 13%N-N- dimethyl
In acetyl amine aqueous solution, after film departs from, deionized water soaks 2d, is placed in 60 DEG C of sterilizing ovens and 8h is dried, and preserves stand-by.
Take certain water factory's water outlet to be test water, processed with institute's masking, after 1d, effect is as follows：
| Before processing concentration | Concentration after process | Clearance | |
| Total plate count | 200CFU/mL | 14CFU/mL | 93.0% |
| MC-RR | 1.5ug/L | 0.26ug/L | 82.7% |
| MC-LR | 1.8ug/L | 0.43ug/L | 76.1% |
Embodiment 7
(1) basement membrane solution is prepared
7g polyethersulfone resin (PES) is added in the beaker A filling 25gN-N- dimethylacetamide solvent, adds
0.4g anhydrous potassium chloride and 4.0g Polyvinylpyrrolidone, are stirred at room temperature, and form basement membrane solution.
(2) graphene oxide solution is prepared
A certain amount of graphene oxide is added in N-N- dimethyl acetylamide, supersound process, forms graphene oxide molten
Liquid, is placed in beaker B, and concentration is 3%.
(3) chitosan solution is prepared
Weigh a certain amount of 5.0g shitosan, add deionized water to be dissolved in beaker C, separately add 10m (1+5)) salpeter solution,
Constant volume in 500mL volumetric flask D, obtains chitosan solution.
(4) casting solution is prepared
Graphene oxide solution 20ml in chitosan solution 25mL and beaker B in volumetric flask D is added to base in beaker A
In coating solution, separately add a small amount of glutaraldehyde solution, stir 6h, stand a few houres, deaeration process is carried out to reactant liquor, obtains casting film
Liquid, stand-by.
(5) film
Under 27 DEG C and 40% damp condition, casting solution in (4) is poured on the glass plate of cleaning, carries out film.
(6) film forming
And then step (5), under the conditions of 20 DEG C, the glass plate level scribbling casting solution are immersed 15%N-N- dimethyl
In acetyl amine aqueous solution, after film departs from, deionized water soaks 2d, is placed in 60 DEG C of sterilizing ovens and 8h is dried, and preserves stand-by.
Take certain water factory's water outlet to be test water, processed with institute's masking, after 1d, effect is as follows：
| Before processing concentration | Concentration after process | Clearance | |
| Total plate count | 200CFU/mL | 10CFU/mL | 95.0% |
| MC-RR | 1.5ug/L | 0.22ug/L | 85.3% |
| MC-LR | 1.8ug/L | 0.38ug/L | 78.9% |
As can be seen that the present invention is good to the removal effect of microorganism in water body and Microcystin in from the above,
Preparation method is simple, the significant increase safety coefficient of drinking water quality.
The above, only presently preferred embodiments of the present invention, not the present invention is made with any pro forma restriction；All
Those skilled in the art, it should be appreciated that the principle of simply explanation invention described in above-described embodiment and description, is not taking off
On the premise of the technology of the present invention spirit and scope, the present invention also have a little change, modify with develop equivalent variations, all according to
According to the present invention substantial technological to the change of any equivalent variations made for any of the above embodiments, modify and develop etc., all should comprise
Within the scope of the present invention.
Claims (10)
1. a kind of modified carbon nano-tube/graphene oxide-shitosan is combined poly (ether-sulfone) ultrafiltration membrane it is characterised in that it is mainly
Using polyether sulfone as supporting layer, CNT or graphene oxide and shitosan are made up of packed layer.
2. modified carbon nano-tube/graphene oxide-the shitosan described in claim 1 is combined the preparation side of poly (ether-sulfone) ultrafiltration membrane
Method is it is characterised in that comprise the following steps：
(1) basement membrane solution is prepared：Polyethersulfone resin is dissolved in organic solvent, adds inorganic substances additive and organic substance
Additive, stirring obtains basement membrane solution；
(2) carbon nano-tube modification：Original CNT CNTs adds supersound process in concentrated acid mixed solution, is washed with deionized water
To neutral, vacuum drying, obtain modified carbon nano-tube；
(3) graphene oxide solution：Graphene oxide is added in organic solvent, supersound process, forms graphene oxide solution；
(4) chitosan solution is prepared:Shitosan is dissolved in deionized water, separately adds salpeter solution, obtains chitosan solution；
(5) casting solution is prepared：Chitosan solution and modified carbon nano-tube or graphene oxide solution are added in basement membrane solution,
Another addition glutaraldehyde solution, after stirring, standing a period of time, carries out deaeration process to reactant liquor, obtains casting solution；
(6) film：Under uniform temperature and damp condition, casting solution is poured on the plate of cleaning, carries out film；
(7) film forming：Under the conditions of uniform temperature, the above-mentioned plate level scribbling casting solution is immersed in organic solution, treats that film departs from
Afterwards, deionized water is soaked, and aseptic drying obtains final product.
3. modified carbon nano-tube/graphene oxide-shitosan according to claim 2 is combined the preparation of poly (ether-sulfone) ultrafiltration membrane
Method it is characterised in that in described step (1) organic solvent be N-N- dimethyl acetylamide, in N-N- dimethylformamide
One or two；Inorganic substances additive is anhydrous Lithium chloride, anhydrous sodium chloride, anhydrous potassium chloride, anhydrous sodium sulfate and no
One or more of water potassium sulfate；Organic substance additive is ethanol, Polyvinylpyrrolidone, isopropanol, in acetone one
Plant or multiple.
4. modified carbon nano-tube/graphene oxide-shitosan according to claim 2 is combined the preparation of poly (ether-sulfone) ultrafiltration membrane
Method it is characterised in that in described step (1), with weight ratio meter, polyethersulfone resin：Organic solvent：Inorganic substances additive：
Organic substance additive=(5-8)：(20-30)：(0.2-0.5)：(2.5-4.0).
5. modified carbon nano-tube/graphene oxide-shitosan according to claim 2 is combined the preparation of poly (ether-sulfone) ultrafiltration membrane
Method it is characterised in that in described step (2) concentrated acid mixed solution be acetic acid, dense H2SO4With dense HNO3Mixed acid, wherein second
Sour, dense H2SO4With dense HNO3Volume range be (2-3)：(2-5)：(0.5-1.5).
6. modified carbon nano-tube/graphene oxide-shitosan according to claim 2 is combined the preparation of poly (ether-sulfone) ultrafiltration membrane
Method it is characterised in that in described step (3) organic solvent be N-N- dimethyl acetylamide, in N-N- dimethylformamide
One or two.
7. modified carbon nano-tube/graphene oxide-shitosan according to claim 2 is combined the preparation of poly (ether-sulfone) ultrafiltration membrane
Method it is characterised in that in described step (3) graphene oxide solution concentration range be 0.1%-3% (g/100ml).
8. modified carbon nano-tube/graphene oxide-shitosan according to claim 2 is combined the preparation of poly (ether-sulfone) ultrafiltration membrane
Method it is characterised in that in described step (4) chitosan solution concentration range be 0.5%-1.0% (g/100ml).
9. modified carbon nano-tube/graphene oxide-shitosan according to claim 2 is combined the preparation of poly (ether-sulfone) ultrafiltration membrane
Method it is characterised in that in described step (5) the addition ratio of each component be：Chitosan solution：Modified carbon nano-tube/oxidation stone
Black alkene solution：Basement membrane solution=(15-25)：(0.3-0.5)/(15-25)：(60-80)(ml：g/ml：ml).
10. modified carbon nano-tube/graphene oxide-the shitosan described in claim 1 is combined the application of poly (ether-sulfone) ultrafiltration membrane, its
It is characterised by, described ultrafilter membrane is used for the removal in household drinking water to microorganism mushroom and Microcystin.
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