CN105214522A - 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
- Publication number
- CN105214522A CN105214522A CN201510579900.0A CN201510579900A CN105214522A CN 105214522 A CN105214522 A CN 105214522A CN 201510579900 A CN201510579900 A CN 201510579900A CN 105214522 A CN105214522 A CN 105214522A
- Authority
- CN
- China
- Prior art keywords
- cnt
- graphene oxide
- polyimides
- separation membrane
- gas separation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000926 separation method Methods 0.000 title claims abstract description 33
- 229920001721 polyimide Polymers 0.000 title claims abstract description 31
- 239000004642 Polyimide Substances 0.000 title claims abstract description 29
- 239000012528 membrane Substances 0.000 title claims abstract description 29
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 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
- 239000006228 supernatant Substances 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 2
- 239000002048 multi walled nanotube Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000004528 spin coating Methods 0.000 claims 1
- 230000035699 permeability Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 239000000463 material 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 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen 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
- 239000002131 composite material Substances 0.000 description 2
- 239000011521 glass 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
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 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
- 239000007788 liquid 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
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 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, be specifically related to a kind of gas separation membrane based on CNT/graphene oxide-polyimides.Its preparation method uses chemical oxidization method to obtain CNT/graphene oxide novel nano carbon structure, a certain amount of CNT/stannic oxide/graphene nano homogenize material is dispersed in dimethylacetylamide, then adding polyimide powder is stirred to evenly, after standing degassed, coating under room temperature is also dry, thus prepares a kind of gas separation membrane based on CNT/graphene oxide-polyimides.Compared to polyimide separation membrane, this gas separation membrane has Heat stability is good, and gas permeability coefficient and separation comparatively high, has important application prospect in gas separation membrane field.
Description
Technical field
The invention belongs to technical field of membrane separation, be specifically related to a kind of gas separation membrane based on CNT/graphene oxide-polyimides and preparation method thereof.
Background technology
Polymeric membrane is because having higher heat endurance and good engineering properties is widely used in gas separaion field.But polymeric gas diffusion barrier exists the Robertson upper limit, have impact on the common raising of gas permeability coefficient and separation, seriously reduce the using value of polymeric gas diffusion barrier.
In order to improve infiltration coefficient and the separation of polymeric membrane simultaneously, researcher is by nano material, as nano titanium oxide, nano silicon and metal-organic framework materials etc., with macromolecule compound, prepare the polymer compound film of gas separating property excellence.But, above-mentioned nano material and high molecular compatibility poor, cause the mechanical performance of polymer compound film to reduce, significantly limit the range of application of such gas separation membrane.In recent years, the novel nano such as CNT and Graphene material with carbon element because of himself excellent properties and with macromolecule good compatibility and being widely used in the preparation of polymeric gas diffusion barrier.The people such as Kim study and find CNT and dimethyl silicone polymer compound [Desalination, 2006,192 (1): 330-339], the people such as Rajabi study and find CNT and polyvinyl chloride compound [JournalofIndustrialandEngineeringChemistry, 2013,19 (1): 347-352], the gas separaion ability of composite separating film can both be improved.But the free volume of single carbon nanotube-polymer compound film is less, be unfavorable for the further raising of gas separating property.
In order to increase the free volume of gas separation membrane, we structurally improve CNT, and the CNT/graphene oxide composite construction that utilized chemical method to prepare first is also applied in polyimide gas separating film.This gas separation membrane is with low cost, has good heat endurance, and higher gas permeability coefficient and separation have important application prospect in gas separation membrane field.
Summary of the invention
The object of this invention is to provide a kind of gas separation membrane based on CNT/graphene oxide-polyimides and preparation method thereof.
Concise and to the point elaboration implementation procedure of the present invention below.First be raw material with oxide/carbon nanometer tube, utilize chemical oxidization method to obtain CNT/graphene oxide, get a certain amount of CNT/graphene oxide ultrasonic disperse in dimethylacetylamide, obtain uniform dispersion liquid.Again a certain amount of polyimides is dissolved in above-mentioned solution, is stirred to and dissolves completely, after standing degassed, apply drying and forming-film on a glass, obtain a kind of gas separation membrane based on CNT/graphene oxide-polyimides.
The preparation method of a kind 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 phosphoric acid, then stir 20 minutes;
(2) 750 milligrams of potassium permanganate are added in the mixed solution described in step (1), stir after 1 hour, stir 2 hours at 60 DEG C;
(3) joining 100 milliliters containing in the ice of 5% hydrogen peroxide by dissolving described in (2), leaving standstill after 14 hours, removing supernatant;
(4) by solution 30% hydrochloric acid cleaning in (3), be then dissolved in by product in 60 milliliter of 30% hydrochloric acid, leave standstill after 12 hours, suction filtration cleaning, to neutral, obtains CNT/graphene oxide;
(5) CNT/graphene oxide of preparation in a certain amount of step (1)-(4) is distributed in dimethylacetylamide, ultrasonic 20 minutes, then add a certain amount of polyimides, be stirred to and dissolve completely, leave standstill 24 hours degassed after, coating and drying and forming-film;
A kind of gas separation membrane based on CNT/graphene oxide-polyimides provided by the present invention.Compared to polyimide separation membrane, this gas separation membrane has good heat endurance, and higher gas permeability coefficient and separation have important application prospect in gas separation membrane field.
Accompanying drawing explanation
Fig. 1 is according to a kind of gas separation membrane schematic diagram based on CNT/graphene oxide-polyimides provided by the present invention.
Fig. 2 is according to the gas separaion result of intrinsic polyimide separation membrane (a) provided by the present invention with compound polyimide diffusion barrier (b) hydrogen, carbon dioxide and nitrogen.
Detailed description of the invention
The present invention is described in detail below in conjunction with accompanying drawing.
150 milligrams of oxide/carbon nanometer tubes are dispersed in 36 milliliters of concentrated sulfuric acids by embodiment 1, after stirring, add 4 milliliters of phosphoric acid, then stir 20 minutes.Then 750 milligrams of potassium permanganate are added in above-mentioned mixed solution, stir after 1 hour, stir 2 hours at 60 DEG C.Afterwards above-mentioned gained solution being joined 100 milliliters of mass fractions is in the ice of 5% hydrogen peroxide, leaves standstill after 14 hours, removing supernatant.Surplus solution 30% hydrochloric acid cleaning, is then dissolved in product in 60 milliliter of 30% hydrochloric acid, leaves standstill after 12 hours, and suction filtration cleaning, to neutral, obtains CNT/graphene oxide.CNT/the graphene oxide of 35 milligrams is distributed in 5 milliliters of dimethylacetylamides, ultrasonic 20 minutes, add 0.74 gram of polyimides again, be stirred to and dissolve completely, leave standstill 24 hours degassed after, to be coated on clean glass plate and drying and forming-film, to obtain a kind of gas separation membrane based on CNT/graphene oxide-polyimides as shown in Figure 1.
Respectively by intrinsic polyimide film and compound polyimide film at 23 DEG C, hydrogen, nitrogen and carbon dioxide is tested respectively under 0.1MPa, as shown in Figure 2, wherein (a) is intrinsic polyimides test result to test result, and (b) is compound polyimide test result.Result shows: the hydrogen of compound polyimide and the gas permeability coefficient of carbon dioxide improve 248.8% and 214.5% respectively than the infiltration coefficient of intrinsic polyimides, improve 158.6% and 161.7% respectively relative to the separation of nitrogen.
Claims (3)
1. the gas separation membrane based on CNT/graphene oxide-polyimides, it is characterized in that: the CNT (2) wrapped up by graphene oxide (1) is dispersed in dimethylacetylamide, after adding polyimides dissolving again, standing, spin-coating film (3), forms a kind of gas separation membrane based on CNT/graphene oxide-polyimides.
2., according to the preparation method of CNT according to claim 1/graphene oxide structure, its step is as follows:
(1) 150 milligrams of oxidation multi-walled carbon nano-tubes are dispersed in 36 milliliters of concentrated sulfuric acids, after stirring, add 4 milliliters of phosphoric acid, then stir 20 minutes;
(2) 750 milligrams of potassium permanganate are added in the mixed solution described in step (1), stir after 1 hour, stir 2 hours at 60 DEG C;
(3) joining 100 milliliters containing in the ice of 5% hydrogen peroxide by dissolving described in (2), leaving standstill after 14 hours, removing supernatant;
(4) by solution 30% hydrochloric acid cleaning in (3), be then dissolved in by product in 60 milliliter of 30% hydrochloric acid, leave standstill after 12 hours, suction filtration cleaning, to neutral, obtains CNT/graphene oxide.
3., according to a kind of gas separation membrane based on CNT/graphene oxide-polyimides according to claim 1, its step is as follows:
(5) CNT/graphene oxide of preparation in a certain amount of step (1)-(4) is distributed in dimethylacetylamide, ultrasonic 20 minutes, then add a certain amount of polyimides, be stirred to and dissolve completely, leave standstill 24 hours degassed after, coating and drying and forming-film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510579900.0A CN105214522B (en) | 2015-09-14 | 2015-09-14 | A kind of gas separation membrane based on CNT/graphene oxide polyimides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510579900.0A CN105214522B (en) | 2015-09-14 | 2015-09-14 | A kind of gas separation membrane based on CNT/graphene oxide polyimides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105214522A true CN105214522A (en) | 2016-01-06 |
| CN105214522B CN105214522B (en) | 2018-02-09 |
Family
ID=54983995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510579900.0A Expired - Fee Related CN105214522B (en) | 2015-09-14 | 2015-09-14 | A kind of gas separation membrane based on CNT/graphene oxide polyimides |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105214522B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107158972A (en) * | 2017-05-10 | 2017-09-15 | 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 |
|---|---|---|---|---|
| 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 |
-
2015
- 2015-09-14 CN CN201510579900.0A patent/CN105214522B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107158972A (en) * | 2017-05-10 | 2017-09-15 | 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105214522B (en) | 2018-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| He et al. | Controlling the selectivity of conjugated microporous polymer membrane for efficient organic solvent nanofiltration | |
| Song et al. | Surface-initiated ARGET ATRP of poly (glycidyl methacrylate) from carbon nanotubes via bioinspired catechol chemistry for efficient adsorption of uranium ions | |
| Liu et al. | Supramolecular hybrid hydrogels from noncovalently functionalized graphene with block copolymers | |
| Ignacz et al. | Ion-stabilized membranes for demanding environments fabricated from polybenzimidazole and its blends with polymers of intrinsic microporosity | |
| CN103372377B (en) | For the preparation method of the imidazole ionic liquid gel supported liquid membrane of gas separaion | |
| Ke et al. | Covalent functionalization of multiwalled carbon nanotubes with a low molecular weight chitosan | |
| Choi et al. | Incorporation of multiwalled carbon nanotubes into poly (vinyl alcohol) membranes for use in the pervaporation of water/ethanol mixtures | |
| CN102391508B (en) | Graphene oxide composite material for flexible electrode and preparation method thereof | |
| CN104028113B (en) | Two filling inorganic particle hybrid film and preparation method and application | |
| CN104004342A (en) | Blocking thermoplastic polyurethane (TPU)/functional graphite oxide composite film and preparation method thereof | |
| CN104672445A (en) | Method for preparing multiwalled carbon nanotube/polyaniline nano composite material | |
| CN104341594A (en) | Preparation method of crosslinked polyimide silicon dioxide mixed gas gel | |
| TW201522519A (en) | Dispersing agent, its preparation method and dispersed composition of carbon-based material comprising the same | |
| CN103785304A (en) | Hydrophilic grafted multiwalled carbon nanotube modified polyvinylidene fluoride film and preparation method thereof | |
| CN104174299A (en) | High-flux positive osmosis membrane based on ultrathin support layer and preparation method thereof | |
| Zhang et al. | Thermally evolved and boron bridged graphene oxide (GO) frameworks constructed on microporous hollow fiber substrates for water and organic matters separation | |
| CN104845381A (en) | Preparation method of modified multi-wall carbon nano-tube material | |
| Haruna et al. | Stabilization of polymer nanocomposites in high-temperature and high-salinity brines | |
| CN105214522A (en) | A kind of gas separation membrane based on CNT/graphene oxide-polyimides | |
| Wang et al. | A highly selective electrochemical sensor for nifedipine based on layer‐by‐layer assembly films from polyaniline and multiwalled carbon nanotube | |
| Wang et al. | Effects of graphene oxide and salinity on sodium deoxycholate hydrogels and their applications in dye absorption | |
| Zhao et al. | Experimental and molecular simulation investigations on interfacial characteristics of gelatin/polyacrylonitrile composite pervaporation membrane | |
| De et al. | Spray‐On Reduced Graphene Oxide‐Poly (vinyl alcohol) Supercapacitors for Flexible Energy and Power | |
| Álvarez-Gómez et al. | Polyacrylonitrile-b-Polystyrene Block Copolymer-Derived Hierarchical Porous Carbon Materials for Supercapacitor | |
| Wang et al. | Covalent organic framework/graphene hybrids: synthesis, properties, and applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180209 |