CN110292869A - A kind of polysulfones/mercapto-modified graphene oxide-carbon nanotube mixed substrate membrane containing nano-grade molecular sieve and preparation method thereof - Google Patents
A kind of polysulfones/mercapto-modified graphene oxide-carbon nanotube mixed substrate membrane containing nano-grade molecular sieve and preparation method thereof Download PDFInfo
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- CN110292869A CN110292869A CN201910559714.9A CN201910559714A CN110292869A CN 110292869 A CN110292869 A CN 110292869A CN 201910559714 A CN201910559714 A CN 201910559714A CN 110292869 A CN110292869 A CN 110292869A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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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
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D71/68—Polysulfones; Polyethersulfones
Abstract
The present invention provides a kind of polysulfones/mercapto-modified (graphene oxide/carbon nanotube) mixed substrate membrane containing nano-grade molecular sieves and preparation method thereof, belong to technology field of membrane materials.Polysulfones provided by the invention/mercapto-modified (graphene oxide/carbon nanotube) mixed substrate membrane containing nano-grade molecular sieve, including polysulfones basilar memebrane, mercapto-modified graphene oxide/carbon nano tube compound material, the mercapto-modified graphene oxide/carbon nano tube compound material is scattered in polysulfones basilar memebrane.The present invention is using mercapto-modified graphene oxide/carbon nano tube compound material as filler, wherein oxygen-containing group is just contained on graphene oxide surface itself, hydrophily is stronger, and after graphene oxide and the composite material modified with mercapto group of carbon nanotube, hydrophily is stronger, there is preferable dispersibility in many polar solvents, and usable multi-solvents are dispersed, preparation process is easily dispersed, and uniform mixed substrate membrane containing nano-grade molecular sieve can be obtained.
Description
Technical field
The present invention relates to technology field of membrane materials more particularly to a kind of polysulfones/mercapto-modified (graphene oxide/carbon is received
Mitron) mixed substrate membrane containing nano-grade molecular sieve and preparation method thereof.
Background technique
Gas membrane Seperation Technology has low energy consumption, Thief zone coefficient, easy to operate and not high to demand to be separated
Feature has obtained extensive concern.But conventional films infiltration coefficient in gas separation cannot be considered in terms of with selection rate, and deposit
In inverse correlation relationship, i.e., the so-called Robeson upper limit limits the development of gas membrane Seperation Technology.
The one kind for the advantages of mixed substrate membrane containing nano-grade molecular sieve is by the way that filler dispersion in the polymer matrix, is had both filler and polymer
Novel film materials.But the main problem that mixed substrate membrane containing nano-grade molecular sieve is faced is that the compatibility of filler and polymer is poor, and exists
Agglomeration traits, it is difficult to prepare the uniform mixed substrate membrane containing nano-grade molecular sieve of filler distribution.
Summary of the invention
The purpose of the present invention is to provide a kind of polysulfones/mercapto-modified (graphene oxide/carbon nanotube) mixed-matrixes
Film and preparation method thereof, in polysulfones provided by the invention/sulfydryl modification graphene oxide/carbon nanotube mixed substrate membrane containing nano-grade molecular sieve filler and
Polymer is easily mixed uniformly, and preparation method is simple.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of polysulfones/mercapto-modified (graphene oxide/carbon nanotube) mixed substrate membrane containing nano-grade molecular sieves, including poly-
Sulfuryl counterdie, mercapto-modified graphene oxide/carbon nano tube compound material, the mercapto-modified graphene oxide/carbon are received
Mitron composite material is scattered in polysulfones basilar memebrane.
Preferably, the mercapto-modified graphene oxide/carbon nano tube compound material is modified by graphene oxide and acid
Carbon nanotube after compound, then carry out sulfydryl modification and obtain；The quality for the carbon nanotube that the graphene oxide and acid are modified
Than for 1:1~10.
Preferably, described poly- in the polysulfones/mercapto-modified (graphene oxide/carbon nanotube) mixed substrate membrane containing nano-grade molecular sieve
The mass percentage of sulfuryl counterdie is 97~99.9%, the matter of mercapto-modified graphene oxide/carbon nano tube compound material
Measuring percentage composition is 0.1~3%.
The present invention also provides the polysulfones described in above-mentioned technical proposal/mercapto-modified (graphene oxides/carbon nanotube)
The preparation method of mixed substrate membrane containing nano-grade molecular sieve, includes the following steps:
Mercapto-modified graphene oxide/carbon nano tube compound material and polysulfones solution are mixed, classification ultrasound point is carried out
It dissipates, then forms a film, obtain polysulfones/mercapto-modified (graphene oxide/carbon nanotube) mixed substrate membrane containing nano-grade molecular sieve.
Preferably, the mixed process includes the following steps:
Mercapto-modified graphene oxide/carbon nano tube compound material is dispersed in polar solvent, sulfydryl modification is obtained
Graphene oxide/carbon nano tube compound material dispersion liquid；
Polysulfones is dissolved in polar solvent, polysulfones solution is obtained；
Mercapto-modified graphene oxide/carbon nano tube compound material dispersion liquid is mixed with polysulfones solution.
Preferably, the polar solvent is N, N'- dimethylformamide.
Preferably, the concentration of polysulfones is 0.01~0.05g/mL in the polysulfones solution.
Preferably, mercapto-modified oxygen in the mercapto-modified graphene oxide/carbon nano tube compound material dispersion liquid
The concentration of graphite alkene is 0.1~1g/L.
Preferably, the classification ultrasonic disperse includes that the level-one ultrasonic disperse, second level ultrasonic disperse, three-level successively carried out surpasses
Sound dispersion and level Four ultrasonic disperse, the power of the level-one ultrasonic disperse are 200~220W, the power of the second level ultrasonic disperse
For 170~190W, the power of the three-level ultrasonic disperse is 140~160W, the power of the level Four ultrasonic disperse is 110~
130W, the level-one ultrasonic disperse, second level ultrasonic disperse, three-level ultrasonic disperse and level Four ultrasonic disperse time independently be 50
~100min.
Preferably, the film forming includes the following steps:
The mixed liquor that the ultrasonic disperse obtains is heated to 60~90 DEG C, be subsequently poured into temperature be 60~90 DEG C at
In pattern tool, through drying, polysulfones/mercapto-modified (graphene oxide/carbon nanotube) mixed substrate membrane containing nano-grade molecular sieve is obtained.
The present invention provides a kind of polysulfones/mercapto-modified (graphene oxide/carbon nanotube) mixed substrate membrane containing nano-grade molecular sieves, including poly-
Sulfuryl counterdie, mercapto-modified graphene oxide/carbon nano tube compound material, the mercapto-modified graphene oxide/carbon are received
Mitron composite material is scattered in polysulfones basilar memebrane.The present invention is with mercapto-modified graphene oxide/carbon nano tube compound material
For filler, wherein oxygen-containing group is just contained on graphene oxide surface itself, and hydrophily is stronger, and graphene oxide and carbon nanotube
Composite material modified with mercapto group after, hydrophily is stronger, there is preferable dispersibility in many polar solvents, can be used a variety of
Solvent is dispersed, and preparation process is easily dispersed, and uniform mixed substrate membrane containing nano-grade molecular sieve can be obtained.In addition, graphene oxide and carbon nanometer
The presence of pipe makes mixed substrate membrane containing nano-grade molecular sieve have more internal gutter, to improve polysulfones/mercapto-modified (graphite oxide
Alkene/carbon nanotube) mixed-matrix membrane separation efficiency.
Detailed description of the invention
The pictorial diagram of 1 gained mixed substrate membrane containing nano-grade molecular sieve of Fig. 1 embodiment；
The pictorial diagram of 2 gained mixed substrate membrane containing nano-grade molecular sieve of Fig. 2 embodiment；
The pictorial diagram of 3 gained mixed substrate membrane containing nano-grade molecular sieve of Fig. 3 embodiment；
The pictorial diagram of 4 gained mixed substrate membrane containing nano-grade molecular sieve of Fig. 4 embodiment；
The pictorial diagram of 1 gained mixed substrate membrane containing nano-grade molecular sieve of Fig. 5 comparative example.
Specific embodiment
The present invention provides a kind of polysulfones/mercapto-modified (graphene oxide/carbon nanotube) mixed substrate membrane containing nano-grade molecular sieves, including poly-
Sulfuryl counterdie, mercapto-modified graphene oxide/carbon nano tube compound material, the mercapto-modified graphene oxide/carbon are received
Mitron composite material is scattered in polysulfones basilar memebrane.In the present invention, the mercapto-modified graphene oxide/carbon nanotube is multiple
It include the carbon nanotube that mercapto-modified graphene oxide and mercapto-modified acid are modified, the mercapto-modified acid in condensation material
Modified carbon nanotube is interspersed between the lamella of mercapto-modified graphene oxide or is attached at mercapto-modified graphite oxide
On the lamella of alkene.
In the present invention, the mercapto-modified graphene oxide/carbon nano tube compound material is preferably by graphene oxide
Modified carbon nanotube is after compound with acid, then carries out sulfydryl modification and obtain；The carbon nanometer that the graphene oxide and acid are modified
The mass ratio of pipe is preferably 1:1~10, more preferably 1:1~5.
In embodiments of the present invention, the preparation method of the mercapto-modified graphene oxide/carbon nano tube compound material
It is preferred that specifically preferably including following steps using the preparation of method disclosed in prior art CN106582532A:
It disperses the modified carbon nanotube of graphene oxide and acid in ethyl alcohol respectively, then mixes, progress ultrasound 1~
2h, then stand 12~for 24 hours after, successively filtered and dried, obtain graphene oxide/carbon nano tube compound material；
Graphene oxide/the carbon nano tube compound material is mixed with ethyl alcohol, successively through ultrasonic disperse and mechanical stirring
Afterwards, it is added acetic acid and 3-mercaptopropyi trimethoxy silane, after stirring 12~for 24 hours, acetone is added, continues 4~6h of stirring, then
It is successively filtered and is dried, obtain mercapto-modified graphene oxide/carbon nano tube compound material.
The present invention first disperses the modified carbon nanotube of graphene oxide and acid in ethyl alcohol respectively, then mixes, into
Row 1~2h of ultrasound, then stand 12~for 24 hours after, then removal supernatant is successively filtered and is dried, obtains graphene oxide/carbon
Nanometer tube composite materials.In the present invention, carbon nanotube can be made to be interspersed between the lamella of graphene oxide in the above process, shape
At graphene oxide/carbon nano tube compound material.
In the present invention, the preparation method of the graphene oxide preferably includes following steps:
At 0~5 DEG C, natural graphite is mixed with the concentrated sulfuric acid, sodium nitrate and potassium permanganate is then added, in 0~10 DEG C of perseverance
Temperature 2.5~4h of stirring, obtains acid mixed solution；
The acid mixed solution is diluted with water 1.8~2.0 times, then stirs 30~40min in 90~100 DEG C of constant temperature
Afterwards, it is diluted to 2.5~3.0 times again with water, continues constant temperature and stir 5~15min, add hydrogen peroxide, insulated and stirred 5~
Centrifuge washing is carried out after 10min, disperses centrifuge washing obtained solid in ethyl alcohol, then 30~60min of ultrasonic vibration is done
It is dry, obtain graphene oxide.
In the present invention, in the preparation process of the graphene oxide, the mass concentration of the concentrated sulfuric acid is preferably 98%；
The concentrated sulfuric acid and natural graphite with than being preferably 25~100mL:1g；The natural graphite and sodium nitrate, potassium permanganate
Mass ratio is preferably 1:0.5~2:3~5；The volume ratio of the hydrogen peroxide and the concentrated sulfuric acid is preferably 1:2~4, the hydrogen peroxide
Mass concentration is preferably 30%；The revolving speed of the centrifuge washing is preferably 8000~1000r/min, the number of the centrifuge washing
To detect supernatant sulfate radical-free ion as standard；The ethyl alcohol is preferably dehydrated alcohol；The power of the ultrasonic vibration is preferred
For 300W；Preferably freeze-day with constant temperature, the temperature of the drying are preferably 60~80 DEG C in a vacuum drying oven for the drying, the time
Preferably 12~for 24 hours, the drying preferably remains normal pressure.
In embodiments of the present invention, the preparation method of the sour modified carbon nano-tube preferably includes following steps:
After carbon nanometer tube material is mixed with acid solution, it is heat-treated, it is then successively washed and dry, it obtains acid and changes
The carbon nanotube of property.
In the present invention, in the sour modifying process, acid solution can be by impurity (such as metal catalytic in carbon nanometer tube material
Agent etc.) it is converted into solable matter, to remove, simultaneously because the strong oxidation of acid, can be such that carbon nano tube surface contains
Oxygen groups.
In the present invention, the carbon nanometer tube material is preferably at least one in multi-walled carbon nanotube and single-walled carbon nanotube
Kind.The present invention is not particularly limited the source of the carbon nanotube, can directly adopt commercially available carbon nanometer tube material.
In the present invention, the acid solution is preferably the mixed acid solution of the concentrated sulfuric acid and concentrated nitric acid, the concentrated sulfuric acid and dense
The volume ratio of nitric acid is preferably 3:1；The concentrated sulfuric acid and concentrated nitric acid are using the conventional concentrated sulfuric acid and concentrated nitric acid, the concentrated sulfuric acid
Mass concentration be preferably 98%；The mass concentration of the concentrated nitric acid is preferably 68%.In the present invention, using above-mentioned mixed acid
Solution can provide oxygen-containing group for the surface of graphene oxide of preparation.
In the present invention, the temperature of the heat treatment is preferably 60~80 DEG C, and the time is preferably 1~3h.
After the completion of heat treatment, the present invention preferably filters heat treatment gained reaction solution, and the carbon after obtained heat treatment is received
Mitron is successively washed and is dried, and the modified carbon nanotube of acid is obtained.
In the present invention, the washing is preferably distilled water with washing lotion；The present invention is not special to the mode of the washing
It limits, can wash to neutrality.
In the present invention, the drying is preferably dried in vacuo, and the vacuum drying temperature is preferably 80~120 DEG C,
Time is preferably 8~12h.
In the present invention, it is preferably by the mode that the modified carbon nanotube of graphene oxide and acid is scattered in respectively in ethyl alcohol
Ultrasound；The power of the ultrasound is preferably 300W, and the time is preferably 2~4h.
In the present invention, it disperses the modified carbon nanotube of graphene oxide and acid in ethyl alcohol respectively, then mixes, into
When row ultrasound, the ultrasonic power is preferably 300W.
In the present invention, described dry in the drying of the graphene oxide obtained after suction filtration/carbon nano tube compound material wet product
Dry preferably freeze-day with constant temperature in a vacuum drying oven, the time of the drying preferably 12~for 24 hours, temperature is preferably 60~80 DEG C,
The drying preferably remains normal pressure.
After obtaining graphene oxide/carbon nano tube compound material, the present invention is compound by the graphene oxide/carbon nanotube
Material is mixed with ethyl alcohol, and successively after ultrasonic disperse and mechanical stirring, acetic acid and 3- mercaptopropyi trimethoxy silane is added,
Stirring 12~for 24 hours after, be added acetone, continue 4~6h of stirring, then successively filtered and dried, obtain mercapto-modified oxidation
Graphene/carbon nanotube composite material.
In the present invention, the graphene oxide/carbon nano tube compound material and acetic acid, 3- mercaptopropyi trimethoxy silicon
The dosage of alkane is preferably 0.1~0.2g:1~2mL:1~5mL；The volume of the acetone and 3-mercaptopropyi trimethoxy silane
Than being preferably 6~25:1.
In the present invention, the graphene oxide/carbon nano tube compound material and the mixed ultrasonic disperse power of ethyl alcohol
Preferably 180~300W, time are preferably 15~30min；The churned mechanically revolving speed is preferably 150r/min, and the time is preferred
For 30~40min, temperature is preferably 25~50 DEG C；The revolving speed stirred after acetic acid and 3- mercaptopropyi trimethoxy silane is added
Preferably 150r/min；The drying preferably freeze-day with constant temperature in a vacuum drying oven, the time of the drying preferably 12~
For 24 hours, temperature is preferably 60~80 DEG C, and the drying preferably remains normal pressure.
In the present invention, in the polysulfones/mercapto-modified (graphene oxide/carbon nanotube) mixed substrate membrane containing nano-grade molecular sieve, institute
The mass percentage for stating polysulfones basilar memebrane is preferably 97~99.9%, more preferably 98~99.8%, most preferably 98.5~
99.5%；The mass percentage of mercapto-modified graphene oxide/carbon nano tube compound material is preferably 0.1~3%, more excellent
It is selected as 0.2~2%, most preferably 0.5~1.5%.
The present invention also provides the polysulfones described in above-mentioned technical proposal/mercapto-modified (graphene oxides/carbon nanotube)
The preparation method of mixed substrate membrane containing nano-grade molecular sieve, includes the following steps:
Mercapto-modified graphene oxide/carbon nano tube compound material and polysulfones solution are mixed, classification ultrasound point is carried out
It dissipates, then forms a film, obtain polysulfones/mercapto-modified (graphene oxide/carbon nanotube) mixed substrate membrane containing nano-grade molecular sieve.
In the present invention, it can effectively avoid ultrasonic power excessive using classification ultrasonic disperse or overlong time causes carbon to be received
Mitron and graphene oxide it is destructurized.
The present invention mixes mercapto-modified graphene oxide/carbon nano tube compound material and polysulfones solution, ultrasonic disperse,
Obtain mixed liquor.
In the present invention, the mixed process preferably includes following steps:
Mercapto-modified graphene oxide/carbon nano tube compound material is dispersed in polar solvent, sulfydryl modification is obtained
Graphene oxide/carbon nano tube compound material dispersion liquid；
Polysulfones is dissolved in polar solvent, polysulfones solution is obtained；
Mercapto-modified graphene oxide/carbon nano tube compound material dispersion liquid is mixed with polysulfones solution.
In the present invention, the polar solvent is preferably N, N'- dimethylformamide.
In the present invention, sulfydryl modification in the mercapto-modified graphene oxide/carbon nano tube compound material dispersion liquid
The concentration of graphene oxide be preferably 0.1~1g/L；Mercapto-modified graphene oxide/the carbon nano tube compound material
The mode being dispersed in polar solvent is preferably ultrasonic disperse；The power of the ultrasonic disperse is preferably 200~220W, and the time is excellent
It is selected as 50~120min.
In the present invention, the temperature of the dissolution is preferably 80~100 DEG C；The process of the dissolution is particularly preferred as to gather
Sulfone is added to polar solvent, in 80~100 DEG C of stirrings to being completely dissolved；The concentration of the polysulfones solution is preferably 0.01~
0.05g/mL；The concentration of polysulfones is preferably 0.01~0.05g/mL in the polysulfones solution.
After obtaining polysulfones solution, the present invention does not preferably cool down, directly with mercapto-modified graphene oxide/carbon nanotube
Composite material dispersion liquid is mixed, and classification ultrasonic disperse is then carried out.
In the present invention, the classification ultrasonic disperse includes the level-one ultrasonic disperse successively carried out, second level ultrasonic disperse, three
Grade ultrasonic disperse and level Four ultrasonic disperse, the power of the level-one ultrasonic disperse are 200~220W, the second level ultrasonic disperse
Power be 170~190W, the power of the three-level ultrasonic disperse is 140~160W, and the power of the level Four ultrasonic disperse is
110~130W, the time independence of the level-one ultrasonic disperse, second level ultrasonic disperse, three-level ultrasonic disperse and level Four ultrasonic disperse
Ground is 50~100min.
After obtaining mixed liquor, the present invention forms a film the mixed liquor, obtains polysulfones/mercapto-modified (oxidation
Graphene/carbon nano-tube) mixed substrate membrane containing nano-grade molecular sieve.
In the present invention, the film forming preferably includes following steps:
The mixed liquor that the ultrasonic disperse obtains is heated to 60~90 DEG C, be subsequently poured into temperature be 60~90 DEG C at
In pattern tool, through drying, mixed substrate membrane containing nano-grade molecular sieve is obtained.
In the present invention, mixed liquor is heated to 60~90 DEG C, pours into the molding die that temperature is 60~90 DEG C, can keeps away
Excessive temperature differentials when exempting to be dried causes gained mixed substrate membrane containing nano-grade molecular sieve cracked；And pour into mixed liquor in molding die, it mixes
Liquid tiles naturally in a mold, and film in homogeneous thickness can be obtained, and the mode for avoiding coating forms a film bring non-uniform film thickness
Even problem.
In the present invention, the molding die is preferably culture dish.
In the present invention, preferably freeze-day with constant temperature, the temperature of the drying are preferably in a vacuum drying oven for the drying
60~90 DEG C, the time is preferably 12~for 24 hours, the drying preferably remains normal pressure.
Below with reference to embodiment to a kind of polysulfones/mercapto-modified (graphene oxide/carbon nanotube) provided by the invention
Mixed substrate membrane containing nano-grade molecular sieve and preparation method thereof is described in detail, but they cannot be interpreted as the limit to the scope of the present invention
It is fixed.
Embodiment 1
1g multi-walled carbon nanotube is distributed in the mixed acid solution of the 30mL concentrated sulfuric acid and 10mL concentrated nitric acid, is stirred at 60 DEG C
Then 3h is washed to neutrality with distillation, in 80 DEG C of normal pressure freeze-day with constant temperature 12h in 80 DEG C of vacuum ovens, obtain what acid was modified
Carbon nanotube；
The concentrated sulfuric acid that 50mL mass concentration is 98% is cooled to 0~5 DEG C, the natural crystalline flake graphite of 2g is added, 0~5
Until being uniformly mixed, 1g sodium nitrate and 6g potassium permanganate, which is then added, and is vigorously stirred simultaneously keeps the temperature of mixture for DEG C stirring
Continue to stir 2.5h at 10 DEG C or less；By gained mixed liquor at 35 DEG C, it is slowly added to 35 DEG C of 95mL of warm deionized water, after
After continuous stirring 30min, it is stirred to react 25min at 90 DEG C, 90 DEG C of warm deionized water is added and is diluted to 280mL, continue to stir
After mixing 5min, hydrogen peroxide (color becomes golden yellow) heat preservation 5min that 25mL mass concentration is 30% is added；Products therefrom is fallen
Enter the speed centrifuge washing in centrifuge tube with 8000r/min, until existing with sulfate radical-free ion in barium chloride detection supernatant；
Centrifuge washing obtained solid is put into the power ultrasound 30min in dehydrated alcohol with 300W, then in 80 DEG C in vacuum oven
Normal pressure freeze-day with constant temperature for 24 hours, obtains graphene oxide；
The modified carbon nanotube of 0.1g graphene oxide and 0.1g acid is mixed with 100mL dehydrated alcohol respectively, in 300W
Ultrasonic 2h obtains graphene oxide dispersion and sour modified carbon nano tube dispersion liquid；By the modified carbon nano tube dispersion liquid of acid
It is added dropwise in graphene oxide dispersion, after 300W ultrasound 1h, stands 12h, then filter, in a vacuum drying oven in 80
DEG C normal pressure freeze-day with constant temperature 12h, obtains graphene oxide/carbon nano tube compound material；
0.2g graphene oxide/carbon nano tube compound material is mixed with 150mL dehydrated alcohol, it is super in the power of 300W
After sound 15min, 30min is stirred in 25 DEG C of revolving speeds with 150r/min, 1mL acetic acid and 2mL 3- mercaptopropyi three is then added
Methoxy silane stirs 12h in the revolving speed of 150r/min, 50mL acetone is then added, continues after stirring 4h, through filtering, by institute
Solid is obtained in a vacuum drying oven in 80 DEG C of normal pressure freeze-day with constant temperature 12h, it is multiple to obtain mercapto-modified graphene oxide/carbon nanotube
Condensation material；
Mercapto-modified graphene oxide/the carbon nano tube compound material of 0.005g and 5mLN, N'- dimethylformamide is mixed
It closes, in room temperature with the power ultrasound 50min of 210W, obtains mercapto-modified graphene oxide/carbon nano tube compound material dispersion
Liquid；0.49g polysulfones is added to 10mLN, in N'- dimethylformamide, in 80 DEG C of magnetic agitation 2h, obtains polysulfones solution；It will
Mercapto-modified graphene oxide/carbon nano tube compound material dispersion liquid is added in polysulfones solution, successively by said mixture
Ultrasound 50min is distinguished under conditions of power is 210W, 180W, 150W and 120W, then in 80 DEG C of heating 10min, then is poured into
It is preheated in 80 DEG C of culture dish, in a vacuum drying oven in 80 DEG C of normal pressure freeze-day with constant temperature 12h, obtains polysulfones/mercapto-modified
(graphene oxide/carbon nanotube) mixed substrate membrane containing nano-grade molecular sieve.
Embodiment 2
0.1g multi-walled carbon nanotube is distributed in the mixed acid solution of the 30mL concentrated sulfuric acid and 1mL concentrated nitric acid, is stirred at 60 DEG C
Then 3h is washed to neutrality with distillation, in a vacuum drying oven in 80 DEG C of normal pressure freeze-day with constant temperature 12h, obtain the modified carbon of acid and receive
Mitron；
The concentrated sulfuric acid that 5mL mass concentration is 98% is cooled to 0~5 DEG C, the natural crystalline flake graphite of 0.2g is added, 0~5
Then DEG C stirring is added 0.1g sodium nitrate and 0.6g potassium permanganate and is vigorously stirred the temperature for making mixture simultaneously until be uniformly mixed
10 DEG C or less are maintained to continue to stir 2.5h；By gained mixed liquor at 35 DEG C, it is slowly added to 9.5mL warm deionized water, is continued
After stirring 30min, it is stirred to react 25min at 90 DEG C, warm deionized water is added and is diluted to 28mL, continue after stirring 5min,
Hydrogen peroxide (color becomes golden yellow) heat preservation 5min that 2mL mass concentration is 30% is added；Products therefrom is poured into centrifuge tube
With the speed centrifuge washing of 8000r/min, until existing with sulfate radical-free ion in barium chloride detection supernatant；By centrifuge washing
Obtained solid is put into the power ultrasound 30min in dehydrated alcohol with 300W, is then dried in vacuo for 24 hours at 80 DEG C, obtains oxidation stone
Black alkene；
The modified carbon nanotube of 0.01g graphene oxide and 0.01g acid is mixed with 10mL dehydrated alcohol respectively, in 300W
Ultrasonic 2h obtains graphene oxide dispersion and sour modified carbon nano tube dispersion liquid；By the modified carbon nano tube dispersion liquid of acid
It is added dropwise in graphene oxide dispersion, after 300W ultrasound 1h, stands 12h, then filter, in a vacuum drying oven in 80
DEG C normal pressure freeze-day with constant temperature 12h, obtains graphene oxide/carbon nano tube compound material；
0.02g graphene oxide/carbon nano tube compound material is mixed with 15mL dehydrated alcohol, it is super in the power of 300W
After sound 15min, 30min is stirred in 25 DEG C of revolving speeds with 150r/min, 1mL acetic acid and 2mL3- mercaptopropyi front three is then added
Oxysilane stirs 12h in the revolving speed of 150r/min, 5mL acetone is then added, continues after stirring 4h, through filtering, gained is consolidated
Body in 80 DEG C of normal pressure freeze-day with constant temperature 12h, obtains mercapto-modified graphene oxide/carbon nanotube composite in a vacuum drying oven
Material；
Mercapto-modified graphene oxide/the carbon nano tube compound material of 0.005g and 5mLN, N'- dimethylformamide is mixed
It closes, in room temperature with the power ultrasound 50min of 210W, obtains mercapto-modified graphene oxide/carbon nano tube compound material dispersion
Liquid；0.49g polysulfones is added to 10mLN, in N'- dimethylformamide, in 80 DEG C of magnetic agitation 2h, obtains polysulfones solution；It will
Mercapto-modified graphene oxide/carbon nano tube compound material dispersion liquid is added in polysulfones solution, successively by said mixture
Ultrasound 50min is distinguished under conditions of power is 210W, 180W, 150W and 120W, then in 80 DEG C of heating 10min, then is poured into
It is preheated in 80 DEG C of culture dish, in a vacuum drying oven in 80 DEG C of normal pressure freeze-day with constant temperature 12h, obtains polysulfones/mercapto-modified
(graphene oxide/carbon nanotube) mixed substrate membrane containing nano-grade molecular sieve.
Embodiment 3
0.5g multi-walled carbon nanotube is distributed in the mixed acid solution of the 15mL concentrated sulfuric acid and 5mL concentrated nitric acid, is stirred at 60 DEG C
Then 3h is washed to neutrality with distillation, in a vacuum drying oven in 80 DEG C of normal pressure freeze-day with constant temperature 12h, obtain the modified carbon of acid and receive
Mitron；
The concentrated sulfuric acid that 25mL mass concentration is 98% is cooled to 0~5 DEG C, the natural crystalline flake graphite of 1g is added, 0~5
Until being uniformly mixed, 0.5g sodium nitrate and 3g potassium permanganate, which is then added, and is vigorously stirred simultaneously protects the temperature of mixture for DEG C stirring
It holds and continues to stir 2.5h at 10 DEG C or less；By gained mixed liquor at 35 DEG C, it is slowly added to 47mL35 DEG C of warm deionized water,
Continue after stirring 30min, be stirred to react 25min at 90 DEG C, add 90 DEG C of warm deionized water and be diluted to 140mL, continues
After stirring 5min, hydrogen peroxide (color becomes golden yellow) heat preservation 5min that 10mL mass concentration is 30% is added；By products therefrom
The speed centrifuge washing in centrifuge tube with 8000r/min is poured into, until being deposited with sulfate radical-free ion in barium chloride detection supernatant
?；Centrifuge washing obtained solid is put into the power ultrasound 30min in dehydrated alcohol with 300W, then in a vacuum drying oven in
80 DEG C of normal pressure freeze-day with constant temperature for 24 hours, obtain graphene oxide；
The modified carbon nanotube of 0.05g graphene oxide and 0.05g acid is mixed with 50mL dehydrated alcohol respectively, in 300W
Ultrasonic 2h obtains graphene oxide dispersion and sour modified carbon nano tube dispersion liquid；By the modified carbon nano tube dispersion liquid of acid
It is added dropwise in graphene oxide dispersion, after 300W ultrasound 1h, stands 12h, then filter, in a vacuum drying oven in 80
DEG C normal pressure freeze-day with constant temperature 12h, obtains graphene oxide/carbon nano tube compound material；
0.1g graphene oxide/carbon nano tube compound material is mixed with 75mL dehydrated alcohol, in the power ultrasound of 300W
After 15min, 30min is stirred in 25 DEG C of revolving speeds with 150r/min, 0.5mL acetic acid and 1mL3- mercaptopropyi front three is then added
Oxysilane stirs 12h in the revolving speed of 150r/min, 25mL acetone is then added, continues after stirring 4h, through filtering, by gained
In 80 DEG C of normal pressure freeze-day with constant temperature 12h, it is compound to obtain mercapto-modified graphene oxide/carbon nanotube in a vacuum drying oven for solid
Material；
By the mercapto-modified graphene oxide/carbon nano tube compound material of 0.0025g and 2.5mLN, N'- dimethyl formyl
Amine mixing, in room temperature with the power ultrasound 50min of 210W, obtains mercapto-modified graphene oxide/carbon nano tube compound material
Dispersion liquid；0.25g polysulfones is added to 5mLN, in N'- dimethylformamide, in 80 DEG C of magnetic agitation 2h, obtains polysulfones solution；
Mercapto-modified graphene oxide/carbon nano tube compound material dispersion liquid is added in polysulfones solution, by said mixture according to
It is secondary that ultrasound 50min is distinguished under conditions of power is 210W, 180W, 150W and 120W, then in 80 DEG C of heating 10min, then fall
Enter in the culture dish for being preheated to 80 DEG C, is placed in a vacuum drying oven, in a vacuum drying oven in 80 DEG C of normal pressure freeze-day with constant temperature 12h,
Obtain polysulfones/mercapto-modified (graphene oxide/carbon nanotube) mixed substrate membrane containing nano-grade molecular sieve.
Embodiment 4
0.5g multi-walled carbon nanotube is distributed in the mixed acid solution of the 15mL concentrated sulfuric acid and 5mL concentrated nitric acid, is stirred at 60 DEG C
Then 3h is washed to neutrality with distillation, in a vacuum drying oven in 80 DEG C of normal pressure freeze-day with constant temperature 12h, obtain the modified carbon of acid and receive
Mitron；
The concentrated sulfuric acid that 25mL mass concentration is 98% is cooled to 0~5 DEG C, the natural crystalline flake graphite of 1g is added, 0~5
Until being uniformly mixed, 0.5g sodium nitrate and 3g potassium permanganate, which is then added, and is vigorously stirred simultaneously protects the temperature of mixture for DEG C stirring
It holds and continues to stir 2.5h at 10 DEG C or less；By gained mixed liquor at 35 DEG C, it is slowly added to 46mL warm deionized water, continues to stir
After mixing 30min, it is stirred to react 25min at 90 DEG C, warm deionized water is added and is diluted to 140mL, continue after stirring 5min,
Hydrogen peroxide (color becomes golden yellow) heat preservation 5min that 10mL mass concentration is 30% is added；Products therefrom is poured into centrifuge tube
In with the speed centrifuge washing of 8000r/min, until existing with sulfate radical-free ion in barium chloride detection supernatant；Centrifugation is washed
It washs obtained solid and is put into power ultrasound 30min in dehydrated alcohol with 300W, then in a vacuum drying oven in 80 DEG C of normal pressure perseverances
Temperature is dry for 24 hours, obtains graphene oxide；
The modified carbon nanotube of 0.05g graphene oxide and 0.1g acid is mixed with 50mL dehydrated alcohol respectively, in 300W
Ultrasonic 2h obtains graphene oxide dispersion and sour modified carbon nano tube dispersion liquid；By the modified carbon nano tube dispersion liquid of acid
It is added dropwise in graphene oxide dispersion, after 300W ultrasound 1h, stands 12h, then filter, in a vacuum drying oven in 80
DEG C normal pressure freeze-day with constant temperature 12h, obtains graphene oxide/carbon nano tube compound material；
0.15g graphene oxide/carbon nano tube compound material is mixed with 75mL dehydrated alcohol, it is super in the power of 300W
After sound 15min, 30min is stirred in 25 DEG C of revolving speeds with 150r/min, 0.5mL acetic acid and 1mL3- mercaptopropyi three is then added
Methoxy silane stirs 12h in the revolving speed of 150r/min, 25mL acetone is then added, continues after stirring 4h, through filtering, by institute
Solid is obtained in a vacuum drying oven in 80 DEG C of normal pressure freeze-day with constant temperature 12h, it is multiple to obtain mercapto-modified graphene oxide/carbon nanotube
Condensation material；
By the mercapto-modified graphene oxide/carbon nano tube compound material of 0.0025g and 2.5mLN, N'- dimethyl formyl
Amine mixing, in room temperature with the power ultrasound 50min of 210W, obtains mercapto-modified graphene oxide/carbon nano tube compound material
Dispersion liquid；0.25g polysulfones is added to 5mLN, in N'- dimethylformamide, in 80 DEG C of magnetic agitation 2h, obtains polysulfones solution；
Mercapto-modified graphene oxide/carbon nano tube compound material dispersion liquid is added in polysulfones solution, by said mixture according to
It is secondary that ultrasound 50min is distinguished under conditions of power is 210W, 180W, 150W and 120W, then in 80 DEG C of heating 10min, then
It pours into the culture dish for being preheated to 80 DEG C, in a vacuum drying oven in 80 DEG C of normal pressure freeze-day with constant temperature 12h, obtains polysulfones/sulfydryl and repair
(graphene oxide/carbon nanotube) mixed substrate membrane containing nano-grade molecular sieve of decorations.
Embodiment 5
2g multi-walled carbon nanotube is distributed in the mixed acid solution of the 60mL concentrated sulfuric acid and 20mL concentrated nitric acid, is stirred at 60 DEG C
Then 4h is washed to neutrality with distillation, in a vacuum drying oven in 80 DEG C of normal pressure freeze-day with constant temperature 12h, obtain the modified carbon of acid and receive
Mitron；
The concentrated sulfuric acid that 100mL mass concentration is 98% is cooled to 0~5 DEG C, the natural crystalline flake graphite of 4g is added, 0~5
To being uniformly mixed, 2g sodium nitrate and 12g potassium permanganate, which is then added, and is vigorously stirred simultaneously keeps the temperature of mixture for DEG C stirring
Continue to stir 2.5h at 10 DEG C or less；By gained mixed liquor at 35 DEG C, it is slowly added to 190mL35 DEG C of warm deionized water, after
After continuous stirring 30min, it is stirred to react 25min at 90 DEG C, 90 DEG C of warm deionized water is added and is diluted to 560mL, continue to stir
After mixing 5min, hydrogen peroxide (color becomes golden yellow) heat preservation 5min that 40mL mass concentration is 30% is added；Products therefrom is fallen
Enter the speed centrifuge washing in centrifuge tube with 8000r/min, until existing with sulfate radical-free ion in barium chloride detection supernatant；
Centrifuge washing obtained solid is put into the power ultrasound 30min in dehydrated alcohol with 300W, then in a vacuum drying oven in 80
DEG C normal pressure freeze-day with constant temperature for 24 hours, obtains graphene oxide；
The modified carbon nanotube of 0.2g graphene oxide and 0.2g acid is mixed with 200mL dehydrated alcohol respectively, in 300W
Ultrasonic 2h obtains graphene oxide dispersion and sour modified carbon nano tube dispersion liquid；By the modified carbon nano tube dispersion liquid of acid
It is added dropwise in graphene oxide dispersion, after 300W ultrasound 1h, stands 12h, then filter, in a vacuum drying oven in 80
DEG C normal pressure freeze-day with constant temperature 12h, obtains graphene oxide/carbon nano tube compound material；
0.4g graphene oxide/carbon nano tube compound material is mixed with 300mL dehydrated alcohol, it is super in the power of 300W
After sound 15min, 30min is stirred in 25 DEG C of revolving speeds with 150r/min, 2mL acetic acid and 4mL3- mercaptopropyi front three is then added
Oxysilane stirs 12h in the revolving speed of 150r/min, 100mL acetone is then added, continues after stirring 4h, through filtering, by gained
Solid in 80 DEG C of dry 12h, obtains mercapto-modified graphene oxide/carbon nano tube compound material in a vacuum drying oven；
By the mercapto-modified graphene oxide/carbon nano tube compound material of 0.001g and 10mLN, N'- dimethylformamide
Mixing obtains mercapto-modified graphene oxide/carbon nano tube compound material point in room temperature with the power ultrasound 50min of 210W
Dispersion liquid；0.98g polysulfones is added to 20mLN, in N'- dimethylformamide, in 80 DEG C of magnetic agitation 2h, obtains polysulfones solution；
Mercapto-modified graphene oxide/carbon nano tube compound material dispersion liquid is added in polysulfones solution, by said mixture according to
It is secondary that ultrasound 50min is distinguished under conditions of power is 210W, 180W, 150W and 120W, then in 80 DEG C of heating 10min, then fall
Enter in the culture dish for being preheated to 80 DEG C, in a vacuum drying oven in 80 DEG C of normal pressure freeze-day with constant temperature 12h, obtains polysulfones/sulfydryl modification
(graphene oxide/carbon nanotube) mixed substrate membrane containing nano-grade molecular sieve.
Comparative example 1
By the commercially available natural flake graphite of 0.05g and 0.05g it is commercially available without laboratory nitration mixture processing carbon nanotube respectively with
The mixing of 50mL dehydrated alcohol, in 300W ultrasound 2h, obtains graphite dispersing solution and carbon nano tube dispersion liquid；By carbon nano tube dispersion liquid
It is added dropwise in graphite dispersing solution, after 300W ultrasound 1h, stands 12h, then filter, in a vacuum drying oven in 80 DEG C of normal pressure perseverances
The dry 12h of temperature, obtains graphite/carbon nanotube mixing material；
0.0025g graphite/carbon nanotube mixing material and 2.5mLN, N'- dimethylformamide are mixed, room temperature with
The power ultrasound 50min of 210W, obtains mercapto-modified graphene oxide/carbon nano tube compound material dispersion liquid；0.25g is gathered
Sulfone is added to 5mLN, in N'- dimethylformamide, in 80 DEG C of magnetic agitation 2h, obtains polysulfones solution；By graphite/carbon nanotube
Mixing material dispersion liquid is added in polysulfones solution, in power is successively 210W, 180W, 150W and 120W by said mixture
Under the conditions of respectively ultrasound 50min, then in 80 DEG C of heating 10min, then pour into the culture dish for being preheated to 80 DEG C, be placed in vacuum do
In dry case, in a vacuum drying oven in 80 DEG C of normal pressure freeze-day with constant temperature 12h, polysulfones/(graphite/carbon nanotube) mixed-matrix is obtained
Film.
Mixed substrate membrane containing nano-grade molecular sieve obtained by Examples 1 to 5 is the uniform black mixed substrate membrane containing nano-grade molecular sieve of color, and is mixed obtained by comparative example 1
It closes in matrix membrane and black reunion occurs.In order to further illustrate, to Examples 1 to 4 and 1 gained mixed substrate membrane containing nano-grade molecular sieve of comparative example into
Row is taken pictures, and gained pictorial diagram is as shown in Fig. 1~5, and wherein Fig. 1~4 are the pictorial diagram of mixed substrate membrane containing nano-grade molecular sieve obtained by Examples 1 to 4, figure
5 be the pictorial diagram of 1 gained mixed substrate membrane containing nano-grade molecular sieve of comparative example, and comparison diagram 1~5 is it is found that mixed substrate membrane containing nano-grade molecular sieve provided by the present invention disperses
Uniformly, and 1 gained mixed substrate membrane containing nano-grade molecular sieve dispersibility of comparative example is poor.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
- A kind of polysulfones/mercapto-modified 1. (graphene oxide/carbon nanotube) mixed substrate membrane containing nano-grade molecular sieve, which is characterized in that including polysulfones Basilar memebrane, mercapto-modified graphene oxide/carbon nano tube compound material, the mercapto-modified graphene oxide/carbon nanometer Pipe composite material is scattered in polysulfones basilar memebrane.
- 2. polysulfones according to claim 1/mercapto-modified (graphene oxide/carbon nanotube) mixed substrate membrane containing nano-grade molecular sieve, special Sign is that the mercapto-modified graphene oxide/carbon nano tube compound material is by graphene oxide and sour modified carbon nanometer Pipe is after compound, then carries out sulfydryl modification and obtain；The graphene oxide and the mass ratio of the modified carbon nanotube of acid be 1:1~ 10。
- Polysulfones according to claim 1 or 2/mercapto-modified 3. (graphene oxide/carbon nanotube) mixed substrate membrane containing nano-grade molecular sieve, It is characterized in that, in the polysulfones/mercapto-modified (graphene oxide/carbon nanotube) mixed substrate membrane containing nano-grade molecular sieve, the polysulfones substrate The mass percentage of film is 97~99.9%, the quality percentage of mercapto-modified graphene oxide/carbon nano tube compound material Content is 0.1~3%.
- The described in any item polysulfones of claims 1 to 3/mercapto-modified 4. (graphene oxide/carbon nanotube) mixed substrate membrane containing nano-grade molecular sieve Preparation method, which comprises the steps of:Mercapto-modified graphene oxide/carbon nano tube compound material and polysulfones solution are mixed, carry out classification ultrasonic disperse, so After form a film, obtain polysulfones/mercapto-modified (graphene oxide/carbon nanotube) mixed substrate membrane containing nano-grade molecular sieve.
- 5. the preparation method according to claim 4, feature is in the mixed process includes the following steps:Mercapto-modified graphene oxide/carbon nano tube compound material is dispersed in polar solvent, mercapto-modified oxygen is obtained Graphite alkene/carbon nano tube compound material dispersion liquid；Polysulfones is dissolved in polar solvent, polysulfones solution is obtained；Mercapto-modified graphene oxide/carbon nano tube compound material dispersion liquid is mixed with polysulfones solution.
- 6. preparation method according to claim 5, which is characterized in that the polar solvent is N, N'- dimethylformamide.
- 7. preparation method according to claim 5, which is characterized in that in the polysulfones solution concentration of polysulfones be 0.01~ 0.05g/mL。
- 8. preparation method according to claim 5, which is characterized in that the mercapto-modified graphene oxide/carbon nanometer The concentration of mercapto-modified graphene oxide is 0.1~1g/L in pipe composite material dispersion liquid.
- 9. the preparation method according to claim 4, which is characterized in that the classification ultrasonic disperse includes one successively carried out Grade ultrasonic disperse, second level ultrasonic disperse, three-level ultrasonic disperse and level Four ultrasonic disperse, the power of the level-one ultrasonic disperse are 200~220W, the power of the second level ultrasonic disperse are 170~190W, the power of the three-level ultrasonic disperse is 140~ 160W, the power of the level Four ultrasonic disperse are 110~130W, the level-one ultrasonic disperse, second level ultrasonic disperse, three-level ultrasound The time of dispersion and level Four ultrasonic disperse independently is 50~100min.
- 10. the preparation method according to claim 4, which is characterized in that the film forming includes the following steps:The mixed liquor that the ultrasonic disperse obtains is heated to 60~90 DEG C, is subsequently poured into the molding die that temperature is 60~90 DEG C In, through drying, obtain polysulfones/mercapto-modified (graphene oxide/carbon nanotube) mixed substrate membrane containing nano-grade molecular sieve.
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