CN106166452A - A kind of gas separation membrane based on CNT/graphene oxide polyether block amide - Google Patents
A kind of gas separation membrane based on CNT/graphene oxide polyether block amide Download PDFInfo
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- CN106166452A CN106166452A CN201610579566.3A CN201610579566A CN106166452A CN 106166452 A CN106166452 A CN 106166452A CN 201610579566 A CN201610579566 A CN 201610579566A CN 106166452 A CN106166452 A CN 106166452A
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- cnt
- graphene oxide
- polyether block
- block amide
- separation membrane
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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
- B01D71/56—Polyamides, e.g. polyester-amides
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Separation Using Semi-Permeable Membranes (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 polyether block amide；Its preparation method is to use chemical oxidization method to obtain CNT/graphene oxide novel nano carbon structure, by a certain amount of CNT/graphene oxide ultrasonic disperse in the mixed solution of ethanol and water (mass ratio 7:3), obtains uniform dispersion liquid A；Being dissolved in by a certain amount of polyether block amide in ethanol and the aqueous solution of above-mentioned equivalent, stirring, to being completely dissolved, obtains dispersion liquid B again；Dispersion liquid A and B is mixed, after standing degassing, pours into drying and forming-film in culture dish, thus prepare a kind of gas separation membrane based on CNT/graphene oxide polyether block amide；A kind of gas separation membrane based on CNT/graphene oxide polyether block amide provided by the present invention；Compared to polyether block amide separation film, this gas separation membrane has preferable heat stability, higher gas permeability coefficient and separation, 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 based on CNT/graphene oxide-polyether block
Gas separation membrane of amide and preparation method thereof.
Background technology
Polymeric membrane is widely used with higher heat stability and separates neck because having good engineering properties at gas
Territory.But, generally there is the Robertson upper limit in polymeric gas separation film, has had a strong impact on gas permeability coefficient and separation
Common raising, reduces the using value of polymeric gas separation film.
In order to improve infiltration coefficient and the separation of polymeric membrane simultaneously, research worker is by nano material, such as nanometer two
Titanium oxide, nano silicon and metal-organic framework materials etc., be combined with macromolecule, prepares gas separating property excellent
Polymer compound film.But, above-mentioned nano material is poor with the high molecular compatibility, causes the mechanicalness of polymer compound film
Can 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 is widely used in polymeric gas separates film because of the excellent properties of himself and the compatibility good with macromolecule
Preparation in.Skoulidas et al. research finds that CNT, because of its smooth inner surface, causes its gas transmission speed score
Son sieves fast 3-4 the order of magnitude [Physical Review Letter, 2002,89,185901], and Shan et al. research finds oxidation
Graphene, can be with selective absorption gas molecule the selectivity improving gas because of its abundant oxygenated functional group
[Nanoscale,2012,4,5477-5482].But, in polymeric matrix, CNT self is prone to reunite, and aoxidizes stone
Ink alkene is prone to fold, is unfavorable for the further raising of gas separating property.
For CNT and the problem of graphene oxide, CNT is structurally improved by we, utilizationization
Method is prepared for CNT/graphene oxide composite construction.This structure has both advantage and to solve both intrinsic
Shortcoming.We are applied in polyether block amide gas separation membrane, prepare CNT/graphene oxide-poly-first
Ether block amides gas separation membrane.This gas separation membrane is with low cost, has preferable heat stability, and higher gas infiltration is
Number and separation, have important application prospect in gas separation membrane field.
Summary of the invention
It is an object of the invention to provide a kind of gas based on CNT/graphene oxide-polyether block amide to separate
Film and preparation method thereof.
The most briefly illustrate that the present invention's realizes process.First with 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 ethanol and water (quality
Than 7:3) mixed solution in, obtain uniform dispersion liquid A；A certain amount of polyether block amide is dissolved in the above-mentioned molten of equivalent again
In liquid, stirring, to being completely dissolved, obtains dispersion liquid B；Dispersion liquid A and B is mixed, after standing degassing, pours in culture dish dry
Dry film forming, obtains a kind of gas separation membrane based on CNT/graphene oxide-polyether block amide.
The preparation of a kind of gas separation membrane based on CNT/graphene oxide-polyether block amide of the present invention
Method, its step is as follows:
(1) 300 milligrams of oxide/carbon nanometer tubes are dispersed in the concentrated sulphuric acid that 80 milliliters of concentration is 16mol/L, stir
After, add 8 milliliters of phosphoric acid, be stirred for 20 minutes；
(2) 1 gram of potassium permanganate is added in the mixed solution described in step (1), after stirring 1 hour, stir at 60 DEG C
Mix 2 hours；
(3) join in 100 milliliters of ice containing 5% hydrogen peroxide, after standing 24 hours, in removing by dissolving described in (2)
Clear liquid；
(4) solution in (3) is cleaned with 30% hydrochloric acid, then product is dissolved in 60 milliliter of 30% hydrochloric acid, stand 12 little
Shi Hou, sucking filtration cleans to neutral, obtains CNT/graphene oxide；
(5) by a certain amount of CNT/graphene oxide ultrasonic disperse of preparation in a certain amount of step (1)-(4) in ethanol
With the mixed solution of water (mass ratio 7:3), obtain uniform dispersion liquid A；Again a certain amount of polyether block amide is dissolved in
Stating in ethanol and the aqueous solution of equivalent, stirring, to being completely dissolved, obtains dispersion liquid B；Dispersion liquid A and B is mixed, stands degassing
After, pour into drying and forming-film in culture dish；
A kind of gas separation membrane based on CNT/graphene oxide-polyether block amide provided by the present invention.Phase
Ratio is in polyether block amide separation film, and this gas separation membrane has a preferable heat stability, higher gas permeability coefficient with point
From coefficient, in gas separation membrane field, there is important application prospect.
Accompanying drawing explanation
Fig. 1 divides according to a kind of gas based on CNT/graphene oxide-polyether block amide provided by the present invention
From film schematic diagram.
Fig. 2 is according to compound polyether block amide separation film gas permeability (a) provided by the present invention and gas-selectively
(b) experimental result.
Detailed description of the invention
Describe the present invention below in conjunction with the accompanying drawings in detail.
300 milligrams of oxide/carbon nanometer tubes are dispersed in the concentrated sulphuric acid that 80 milliliters of concentration is 16mol/L, stirring by embodiment 1
After Jun Yun, add 8 milliliters of phosphoric acid, be stirred for 20 minutes；1 gram of potassium permanganate is added in the mixed solution described in step (1),
After stirring 1 hour, stir 2 hours at 60 DEG C；Join in 100 milliliters of ice containing 5% hydrogen peroxide by dissolving described in (2),
After standing 24 hours, remove supernatant；Solution in (3) is cleaned with 30% hydrochloric acid, then product is dissolved in 60 milliliter of 30% salt
In acid, after standing 12 hours, sucking filtration cleans to neutral, obtains CNT/graphene oxide；By a certain amount of step (1)-(4)
A certain amount of CNT/graphene oxide the ultrasonic disperse of middle preparation, in the mixed solution of ethanol and water (mass ratio 7:3), obtains
To uniform dispersion liquid A；Being dissolved in by a certain amount of polyether block amide in ethanol and the aqueous solution of above-mentioned equivalent, stirring is to the completeest again
CL, obtains dispersion liquid B；Dispersion liquid A and B is mixed, after standing degassing, pours into drying and forming-film in culture dish；Obtain one
Plant gas separation membrane based on CNT/graphene oxide-polyether block amide as shown in Figure 1.
By intrinsic polyether block amide film and compound polyether block amide film at 35 DEG C, test respectively under 0.4MPa methane,
Nitrogen and carbon dioxide, test result is as in figure 2 it is shown, result shows: the gas of the carbon dioxide of compound polyether block amide oozes
Coefficient is 179barrer thoroughly, is respectively 80 and 23 relative to the separation of nitrogen Yu methane, far above intrinsic polyether block acyl
The separating property of amine, and exceed well over the Robertson upper limit of report in 2008.
Claims (1)
1. gas separation membrane based on CNT/graphene oxide-polyether block amide and preparation method thereof, its step
As follows:
(1) 300 milligrams of oxide/carbon nanometer tubes are dispersed in the concentrated sulphuric acid that 80 milliliters of concentration is 16mol/L, after stirring, add
Enter 8 milliliters of phosphoric acid, be stirred for 20 minutes；
(2) 1 gram of potassium permanganate is added in the mixed solution described in step (1), after stirring 1 hour, at 60 DEG C, stir 2 little
Time；
(3) join in 100 milliliters of ice containing 5% hydrogen peroxide by dissolving described in (2), after standing 24 hours, remove supernatant；
(4) solution in (3) is cleaned with 30% hydrochloric acid, then product is dissolved in 60 milliliter of 30% hydrochloric acid, after standing 12 hours,
Sucking filtration cleans to neutral, obtains CNT/graphene oxide；
(5) by a certain amount of CNT/graphene oxide ultrasonic disperse of preparation in a certain amount of step (1)-(4) in ethanol and water
In the mixed solution of (mass ratio 7:3), obtain uniform dispersion liquid A；Again a certain amount of polyether block amide is dissolved in above-mentioned etc.
The ethanol of amount is with aqueous solution, and stirring, to being completely dissolved, obtains dispersion liquid B；Dispersion liquid A and B is mixed, after standing degassing, inclines
Note drying and forming-film in culture dish.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610579566.3A CN106166452A (en) | 2016-07-22 | 2016-07-22 | A kind of gas separation membrane based on CNT/graphene oxide polyether block amide |
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| CN201610579566.3A CN106166452A (en) | 2016-07-22 | 2016-07-22 | A kind of gas separation membrane based on CNT/graphene oxide polyether block amide |
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| CN106166452A true CN106166452A (en) | 2016-11-30 |
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| CN201610579566.3A Pending CN106166452A (en) | 2016-07-22 | 2016-07-22 | A kind of gas separation membrane based on CNT/graphene oxide polyether block amide |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107221387A (en) * | 2017-05-05 | 2017-09-29 | 华侨大学 | The preparation method of High conductivity graphene film based on transience framework |
| CN107413209A (en) * | 2017-06-09 | 2017-12-01 | 中国石油大学(华东) | A kind of gas separation membrane based on molybdenum disulfide/CNT polyether block amide |
| CN110142027A (en) * | 2019-04-28 | 2019-08-20 | 中国工程物理研究院材料研究所 | A kind of room temperature inhales hydrogen carbon aerogels material and preparation method thereof |
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| CN102451621A (en) * | 2010-10-27 | 2012-05-16 | 中国科学院大连化学物理研究所 | Polyether-b-polyamide multilayer composite film and preparation method thereof |
| CN103100313A (en) * | 2011-11-15 | 2013-05-15 | 中国科学院大连化学物理研究所 | Polyether-b-polyamide (PEBA)/polyethyleneglycol (PEG) or polyoxyethylene (PEO) blend membrane, and preparation and application thereof |
| CN105214522A (en) * | 2015-09-14 | 2016-01-06 | 中国石油大学(华东) | A kind of gas separation membrane based on CNT/graphene oxide-polyimides |
| CN105396432A (en) * | 2015-10-30 | 2016-03-16 | 郑州大学 | Graphene oxide/Pebax hollow fiber membrane and preparation method thereof |
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2016
- 2016-07-22 CN CN201610579566.3A patent/CN106166452A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102451621A (en) * | 2010-10-27 | 2012-05-16 | 中国科学院大连化学物理研究所 | Polyether-b-polyamide multilayer composite film and preparation method thereof |
| CN103100313A (en) * | 2011-11-15 | 2013-05-15 | 中国科学院大连化学物理研究所 | Polyether-b-polyamide (PEBA)/polyethyleneglycol (PEG) or polyoxyethylene (PEO) blend membrane, and preparation and application thereof |
| CN105214522A (en) * | 2015-09-14 | 2016-01-06 | 中国石油大学(华东) | A kind of gas separation membrane based on CNT/graphene oxide-polyimides |
| CN105396432A (en) * | 2015-10-30 | 2016-03-16 | 郑州大学 | Graphene oxide/Pebax hollow fiber membrane and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107221387A (en) * | 2017-05-05 | 2017-09-29 | 华侨大学 | The preparation method of High conductivity graphene film based on transience framework |
| CN107221387B (en) * | 2017-05-05 | 2020-07-10 | 华侨大学 | Preparation method of high-conductivity graphene film based on transient framework |
| CN107413209A (en) * | 2017-06-09 | 2017-12-01 | 中国石油大学(华东) | A kind of gas separation membrane based on molybdenum disulfide/CNT polyether block amide |
| CN107413209B (en) * | 2017-06-09 | 2020-10-20 | 中国石油大学(华东) | Gas separation membrane based on molybdenum disulfide/carbon nanotube-polyether block amide |
| CN110142027A (en) * | 2019-04-28 | 2019-08-20 | 中国工程物理研究院材料研究所 | A kind of room temperature inhales hydrogen carbon aerogels material and preparation method thereof |
| CN110142027B (en) * | 2019-04-28 | 2022-04-29 | 中国工程物理研究院材料研究所 | Room-temperature hydrogen-absorbing carbon aerogel material and preparation method thereof |
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