CN105214522B - A kind of gas separation membrane based on CNT/graphene oxide polyimides - Google Patents
A kind of gas separation membrane based on CNT/graphene oxide polyimides Download PDFInfo
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- CN105214522B CN105214522B CN201510579900.0A CN201510579900A CN105214522B CN 105214522 B CN105214522 B CN 105214522B CN 201510579900 A CN201510579900 A CN 201510579900A CN 105214522 B CN105214522 B CN 105214522B
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- cnt
- graphene oxide
- separation membrane
- polyimides
- gas separation
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- 238000000926 separation method Methods 0.000 title claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229920001721 polyimide Polymers 0.000 title claims abstract description 28
- 239000004642 Polyimide Substances 0.000 title claims abstract description 26
- 239000012528 membrane Substances 0.000 title claims abstract description 25
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000007872 degassing Methods 0.000 claims abstract description 5
- 229940113088 dimethylacetamide Drugs 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 2
- 239000002048 multi walled nanotube Substances 0.000 claims 1
- 230000035699 permeability Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract 2
- 229910021392 nanocarbon Inorganic materials 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000013105 nano metal-organic framework Substances 0.000 description 1
- 239000013289 nano-metal-organic framework Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to technical field of membrane separation, and in particular to a kind of gas separation membrane based on CNT/graphene oxide polyimides.Its preparation method is to obtain CNT/graphene oxide novel nano carbon structure using chemical oxidization method, a certain amount of CNT/stannic oxide/graphene nano material is dispersed in dimethyl acetamide, then polyimide powder is added to be stirred until homogeneous, after standing degassing, coat and dry at room temperature, so as to prepare a kind of gas separation membrane based on CNT/graphene oxide polyimides.Compared to polyimide separation membrane, the gas separation membrane has the features such as heat endurance is good, gas permeability coefficient and higher separation, has important application prospect in gas separation membrane field.
Description
Technical field
The invention belongs to technical field of membrane separation, and in particular to one kind is based on CNT/graphene oxide-polyimides
Gas separation membrane and preparation method thereof.
Background technology
Polymeric membrane is led because being widely used to separate in gas with higher heat endurance and good engineering properties
Domain.However, polymeric gas seperation film has the Robertson upper limit, carrying jointly for gas permeability coefficient and separation have impact on
Height, seriously reduce the application value of polymeric gas seperation film.
In order to improve the infiltration coefficient and separation of polymeric membrane simultaneously, researcher is by nano material, such as nanometer two
Titanium oxide, nano silicon and metal-organic framework materials etc., it is compound with macromolecule, it is excellent to prepare gas separating property
Polymer compound film.However, above-mentioned nano material and high molecular compatibility are poor, cause the mechanicalness of polymer compound film
It can reduce, significantly limit the application of such gas separation membrane.In recent years, the novel nano such as CNT and graphene
Carbon material is widely used in polymeric gas seperation film because of the excellent properties of its own and the compatibility good with macromolecule
Preparation in.Kim et al. research find by CNT and dimethyl silicone polymer it is compound [Desalination, 2006,192
(1):330-339], Rajabi et al. researchs are found CNT and compound [the Journal of Industrial of polyvinyl chloride
and Engineering Chemistry,2013,19(1):347-352], the gas that can improve composite separating film separates
Ability.However, the free volume of single carbon nanotube-polymer compound film is smaller, it is unfavorable for the further of gas separating property
Improve.
In order to increase the free volume of gas separation membrane, we are improved in structure to CNT, utilize first
Chemical method is prepared for CNT/graphene oxide composite construction and applied in polyimide gas separating film.The gas
Body seperation film cost is cheap, has preferable heat endurance, higher gas permeability coefficient and separation, in gas separation membrane
Field has important application prospect.
The content of the invention
It is an object of the invention to provide a kind of gas separation membrane based on CNT/graphene oxide-polyimides and
Its preparation method.
The implementation process of the present invention is briefly illustrated below.First using oxide/carbon nanometer tube as raw material, chemical oxidation is utilized
Legal system obtains CNT/graphene oxide, takes a certain amount of CNT/graphene oxide ultrasonic disperse in dimethyl acetamide,
Obtain uniform dispersion liquid.A certain amount of polyimides is dissolved in above-mentioned solution again, stirring stands degassing to being completely dissolved
Afterwards, drying and forming-film on a glass is applied, obtains a kind of gas separation based on CNT/graphene oxide-polyimides
Film.
A kind of preparation method of gas separation membrane based on CNT/graphene oxide-polyimides of the present invention,
Its step is as follows:
(1) 150 milligrams of oxide/carbon nanometer tubes are dispersed in 36 milliliters of concentrated sulfuric acids, after stirring, add 4 milliliters of phosphorus
Acid, it is stirred for 20 minutes;
(2) 750 milligrams of potassium permanganate are added in the mixed solution described in step (1), after stirring 1 hour, at 60 DEG C
Lower stirring 2 hours;
(3) dissolving described in (2) is added in 100 milliliters of ice containing 5% hydrogen peroxide, after standing 14 hours, in removing
Clear liquid;
(4) solution in (3) is cleaned with 30% hydrochloric acid, then product is dissolved in 60 milliliter of 30% hydrochloric acid, it is small to stand 12
Shi Hou, cleaning is filtered to neutrality, obtains CNT/graphene oxide;
(5) CNT/graphene oxide prepared in a certain amount of step (1)-(4) is distributed to dimethyl acetamide
In, ultrasound 20 minutes, a certain amount of polyimides is added, stirring after standing degassing in 24 hours, is coated and done to being completely dissolved
Dry film forming;
A kind of gas separation membrane based on CNT/graphene oxide-polyimides provided by the present invention.Compared to
Polyimide separation membrane, the gas separation membrane have a preferable heat endurance, higher gas permeability coefficient and separation,
Gas separation membrane field has important application prospect.
Brief description of the drawings
Fig. 1 is according to a kind of gas separation membrane based on CNT/graphene oxide-polyimides provided by the present invention
Schematic diagram.
Fig. 2 is according to intrinsic polyimide separation membrane (a) provided by the present invention and compound polyimide seperation film (b) hydrogen
The gas separating resulting of gas, carbon dioxide and nitrogen.
Embodiment
It is described in detail the present invention below in conjunction with the accompanying drawings.
Embodiment 1,150 milligrams of oxide/carbon nanometer tubes are dispersed in 36 milliliters of concentrated sulfuric acids, after stirring, add 4 millis
Phosphoric acid is risen, is stirred for 20 minutes.Then 750 milligrams of potassium permanganate are added in above-mentioned mixed solution, after stirring 1 hour,
Stirred 2 hours at 60 DEG C.Above-mentioned resulting solution is added in the ice that 100 milliliters of mass fractions are 5% hydrogen peroxide, stood afterwards
After 14 hours, supernatant is removed.Surplus solution is cleaned with 30% hydrochloric acid, and then product is dissolved in 60 milliliter of 30% hydrochloric acid, quiet
After putting 12 hours, cleaning is filtered to neutrality, obtains CNT/graphene oxide.By 35 milligrams of CNT/graphite oxide
Alkene is distributed in 5 milliliters of dimethyl acetamides, ultrasound 20 minutes, adds 0.74 gram of polyimides, and stirring is quiet to being completely dissolved
After putting degassing in 24 hours, coated on clean glass plate and drying and forming-film, obtaining a kind of being based on CNT/graphite oxide
The gas separation membrane of alkene-polyimides is as shown in Figure 1.
Respectively intrinsic polyimide film and compound polyimide film are tested into hydrogen, nitrogen respectively at 23 DEG C under 0.1MPa
And carbon dioxide, for test result as shown in Fig. 2 wherein (a) is intrinsic polyimides test result, (b) is compound polyimide
Test result.As a result show:The hydrogen of compound polyimide and the intrinsic polyimides of gas permeability coefficient ratio of carbon dioxide
248.8% and 214.5% has been respectively increased in infiltration coefficient, and 158.6% He has been respectively increased relative to the separation of nitrogen
161.7%.
Claims (1)
1. a kind of preparation method of the gas separation membrane based on CNT/graphene oxide-polyimides, its step include:
(1) 150 milligrams of oxidation multi-wall carbon nano-tube tubes are dispersed in 36 milliliters of concentrated sulfuric acids, after stirring, add 4 milliliters of phosphorus
Acid, it is stirred for 20 minutes, obtains mixed solution A;
(2) 750 milligrams of potassium permanganate are added in the mixed solution A described in step (1), after stirring 1 hour, stirred at 60 DEG C
Mix 2 hours, obtain mixed solution B;
(3) will be added in mixed solution B described in (2) in 100 milliliters of ice containing 5% hydrogen peroxide, after standing 14 hours, in removing
Clear liquid, obtain mixture C;
(4) mixture C in (3) is cleaned with 30% hydrochloric acid, then product is scattered in 60 milliliter of 30% hydrochloric acid, it is small to stand 12
Shi Hou, cleaning is filtered to neutrality, obtains CNT/graphene oxide of high oxidation degree;
(5) CNT/graphene oxide prepared in a certain amount of step (1)-(4) is distributed in dimethyl acetamide, surpassed
Sound 20 minutes, a certain amount of polyimides is added, stirring after standing degassing in 24 hours, is coated and is dried to being completely dissolved
Film.
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CN105214522B true CN105214522B (en) | 2018-02-09 |
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CN106166452A (en) * | 2016-07-22 | 2016-11-30 | 中国石油大学(华东) | A kind of gas separation membrane based on CNT/graphene oxide polyether block amide |
CN107158972B (en) * | 2017-05-10 | 2019-07-23 | 浙江工商大学 | A kind of Nano carbon balls-polyimides binary gas separation mixed substrate membrane containing nano-grade molecular sieve and preparation method thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103122075A (en) * | 2013-03-19 | 2013-05-29 | 苏州格瑞丰纳米科技有限公司 | High heat-conducting thin graphene-based composite material, as well as preparation method and application thereof |
CN103832996A (en) * | 2012-11-23 | 2014-06-04 | 海洋王照明科技股份有限公司 | Graphene/carbon nano-tube composite material, preparation method and application thereof |
CN103864069A (en) * | 2014-03-26 | 2014-06-18 | 天津师范大学 | Method for preparing graphene by taking carbon nanotubes with discontinuous tube walls as raw materials |
WO2014120162A1 (en) * | 2013-01-30 | 2014-08-07 | Empire Technology Development, Llc | Carbon nanotube-graphene composite |
CN104028113A (en) * | 2014-06-27 | 2014-09-10 | 天津大学 | Double-filled inorganic particle hybrid membrane as well as preparation method and application thereof |
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CN103832996A (en) * | 2012-11-23 | 2014-06-04 | 海洋王照明科技股份有限公司 | Graphene/carbon nano-tube composite material, preparation method and application thereof |
WO2014120162A1 (en) * | 2013-01-30 | 2014-08-07 | Empire Technology Development, Llc | Carbon nanotube-graphene composite |
CN103122075A (en) * | 2013-03-19 | 2013-05-29 | 苏州格瑞丰纳米科技有限公司 | High heat-conducting thin graphene-based composite material, as well as preparation method and application thereof |
CN103864069A (en) * | 2014-03-26 | 2014-06-18 | 天津师范大学 | Method for preparing graphene by taking carbon nanotubes with discontinuous tube walls as raw materials |
CN104028113A (en) * | 2014-06-27 | 2014-09-10 | 天津大学 | Double-filled inorganic particle hybrid membrane as well as preparation method and application thereof |
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