CN105749769B - A kind of preparation and application of ionic liquid blend film - Google Patents
A kind of preparation and application of ionic liquid blend film Download PDFInfo
- Publication number
- CN105749769B CN105749769B CN201610235201.9A CN201610235201A CN105749769B CN 105749769 B CN105749769 B CN 105749769B CN 201610235201 A CN201610235201 A CN 201610235201A CN 105749769 B CN105749769 B CN 105749769B
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- ionic liquid
- polyoxyethylene
- blend film
- type ion
- room temperature
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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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
-
- 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
-
- 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
- B01D67/0002—Organic membrane manufacture
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The invention discloses the preparation method and applications that a kind of ionic liquid is blended, and belong to gas separation membrane technical field.Its preparation process includes: to prepare polyoxyethylene-polycaprolactam block copolymer solution, and imidazole type ionic liquid at room temperature is added in the solution, and casting solution is made；It dries, and is further dried under vacuum conditions at room temperature.The present invention has the advantages that preparation method is simple, ionic liquid is fixed in macromolecular chain, and turnover rate is low.Obtained composite membrane is separated for gas, has excellent comprehensive performance.Particularly, there is high CO using the blend film of 40% mass fraction 1- butyl -2,3- methylimidazole hexafluorophosphate of filling2Infiltration rate and CO2/CH4、CO2/N2Selective, pure gas tests CO under humidified condition2Infiltration coefficient is up to 695Barrer, CO2/CH4Selectivity is 35, CO2/N2Selectivity is 42.
Description
Technical field
The present invention relates to the preparations and application of a kind of ionic liquid blend film, belong to gas membrane Seperation Technology field.
Background technique
In recent years, with the development of industry, combustion of fossil fuel produces a large amount of CO2Gas.At present be badly in need of efficiently it is low at
This carbon capture technology.Membrane technology due to green, low energy consumption, equipment investment is low etc., and advantages are got the attention, be to have at present
Hope one of the technology used on a large scale.At present since membrane material separating property is not high, limits it and further develop.Design preparation
Have high osmosis and highly selective membrane material is the hot spot studied at present.Conventional polymer material has good filming performance
It is the main body of membrane material with inexpensive feature.But permeability and selective shifting trade-off effect limit membrane material
The application of material is to continue to lift up permeability of the membrane and selectivity based on high molecular research.
Ionic liquid especially ionic liquid at room temperature is a kind of material for being preferably applied to carbon capture due to low volatility
Material, has had obtained relatively broad application in absorption field.Ionic liquid film is mainly prepared as supported liquid membrane at present, mechanical steady
Qualitative poor, especially under high pressure, ionic liquid is easy to be lost.Ionic liquid is blended with high molecular material, utilizes height
Strong and weak interaction between molecule segment and particle liquid is a kind of effective method to prepare membrane material.Ion at present
Liquid and polymer blended film have certain applications and gas separation field, are gathered in oneself with the good polyoxyethylene-of filming performance
Amide block copolymers are expected to improve the stability of ionic liquid as main body.Especially for imidazole type ion liquid, it is total to
After being mixed in macromolecule, the faciliated diffusion effect of imidazole group can be played under humidified condition, to significantly improve the separation of film
Performance.
Summary of the invention
It is an object of the invention to a kind of preparation method and application of ionic liquid blend film.The ion prepared in this approach
Liquid blend film is for separating CO2/CH4、CO2/N2Mixture, CO with higher2Infiltration rate and separation factor.
A kind of ionic liquid blend film proposed by the present invention, main component are polyoxyethylene-polycaprolactam block copolymerization
Object and imidazole type ion liquid；Wherein, the mass fraction of imidazole type ion liquid is 5-50%.
Wherein, the imidazole type ion liquid is 1- butyl -2,3- methylimidazole hexafluorophosphate, -3 methyl of 1- butyl
Tetrafluoroborate, -3 methylimidazole dicyan amine salt of 1- butyl any in 1- ethyl-3-methylimidazole bis trifluoromethyl salt contain
The ionic liquid at room temperature of imidazoles.
The method for preparing above-mentioned ionic liquid blend film, comprising the following steps:
Step 1: polyoxyethylene-the polycaprolactam for being 55-60% by the polyoxyethylene segment mass fraction of certain mass
Block copolymer is added in the ethanol solution that mass fraction is 65-75%, is heated at reflux to 75~90 DEG C, makes polyoxy second therein
Alkene-polycaprolactam block copolymer is completely dissolved, and is cooled to room temperature, and the polyoxyethylene-that mass fraction is 2-7% is made and gathers oneself
Lactams block copolymer solution；
Step 2: taking polyoxyethylene-polycaprolactam block copolymer solution of certain mass, it is added dropwise to imidazole type ion
Mixed solution A is made in liquid, wherein the imidazole type ion liquid accounts for polyoxyethylene-polycaprolactam block copolymer matter
Amount score is 5-50%, and magnetic agitation is completely dissolved imidazole type ion liquid therein, is cooled to room temperature obtained casting solution；
Step 3: casting solution made from step 2 is added in polytetrafluoroethylene (PTFE) culture dish, film-forming at room temperature, in
Dry 24~48h is under 35-60 DEG C of vacuum condition to get ionic liquid blend film.
Ionic liquid blend film of the invention is used in gas separation, in particular for CO2/CH4Or CO2/N2Point
From.
The present invention has the advantages that preparation method is simple, ionic liquid is fixed in macromolecular chain, and turnover rate is low.It is made
The composite membrane obtained is separated for gas, has excellent comprehensive performance.Particularly, using filling 50% mass fraction 1- butyl-
The blend film of 2,3- methylimidazole hexafluorophosphates has high CO2Infiltration rate and CO2/CH4、CO2/N2Selectivity, humidification
Under the conditions of pure gas test CO2Infiltration coefficient is up to 695Barrer, CO2/CH4Selectivity is 35, CO2/N2Selectivity is 42.
Specific embodiment
Technical solution of the present invention is described in further detail combined with specific embodiments below, described specific embodiment
Only the present invention is explained, is not intended to limit the invention.
Embodiment 1, a kind of preparation of ionic liquid blend film, comprising the following steps:
Step 1: weigh 0.5g polyoxyethylene-polycaprolactam block copolymer (trade name Pebax 1657), 7g without
Water-ethanol and 3g deionized water are added in the three-necked flask with condenser pipe, in 80 DEG C of water bath with thermostatic control, with the speed of 500r/min
Return stirring 2h is spent, dissolves polyoxyethylene therein-polycaprolactam block copolymer all.
Step 2: weighing 0.25g 1- butyl -2,3- methylimidazole hexafluorophosphate, it is added dropwise made from step 1
In polyoxyethylene-polycaprolactam block copolymer solution, with the speed magnetic agitation 2h of 1000r/min, it is cooled to room temperature system
Obtain casting solution；
Step 3: by being poured into after casting solution standing and defoaming in clean polytetrafluoroethylene (PTFE) culture dish (Φ 100mm), room temperature
Lower drying film-forming for 24 hours, then under 45 DEG C, vacuum condition it is dry for 24 hours, obtain about 100 μm of thickness of ionic liquid and be blended
Film.
By ionic liquid blend film obtained above under conditions of room temperature, test pressure are 2bar, added with pure gas
It is tested under the conditions of wet, CO2Infiltration coefficient is 695barrer (1barrer=10-10cm3(STP)cm/(cm2S cmHg)), CO2/N2
Separation factor is 42, CO2/CH4Separation factor is 35.
Embodiment 2, a kind of preparation of ionic liquid blend film, preparation process and embodiment 1 are almost the same, and difference exists
In: the quality of 1- butyl -2,3- methylimidazole hexafluorophosphate is 0.025g in step 2.
Test condition is same as Example 1, is tested under humidified condition with pure gas, CO2Infiltration coefficient is 484barrer
(1barrer=10-10cm3(STP)cm/(cm2S cmHg)), CO2/N2Separation factor is 26, CO2/CH4Separation factor is 22.
Embodiment 3, a kind of preparation of ionic liquid blend film, preparation process and embodiment 1 are almost the same, and difference exists
In: the quality of 1- butyl -2,3- methylimidazole hexafluorophosphate is 0.10g in step 2.
Test condition is same as Example 1, is tested under humidified condition with pure gas, CO2Infiltration coefficient is 580barrer
(1barrer=10-10cm3(STP)cm/(cm2S cmHg)), CO2/N2Separation factor is 31, CO2/CH4Separation factor is 33.
Embodiment 4, a kind of preparation of ionic liquid blend film, preparation process and embodiment 1 are almost the same, and difference exists
In: in step 2, imidazole type ion liquid is -3 methyl imidazolium tetrafluoroborate of 1- butyl, quality 0.25g.
Test condition is same as Example 1, is tested under humidified condition with pure gas, CO2Infiltration coefficient is 553barrer
(1barrer=10-10cm3(STP)cm/(cm2S cmHg)), CO2/N2Separation factor is 38, CO2/CH4Separation factor is 30.
Embodiment 5, a kind of preparation of ionic liquid blend film, preparation process and embodiment 1 are almost the same, and difference exists
In: in step 2, imidazole type ion liquid is -3 methylimidazole dicyan amine salt of 1- butyl, quality 0.25g.
Test condition is same as Example 1, is tested under humidified condition with pure gas, CO2Infiltration coefficient is 496barrer
(1barrer=10-10cm3(STP)cm/(cm2S cmHg)), CO2/N2Separation factor is 34, CO2/CH4Separation factor is 26.
Embodiment 6, a kind of preparation of ionic liquid blend film, preparation process and embodiment 1 are almost the same, and difference exists
In: in step 2, imidazole type ion liquid is 1- ethyl-3-methylimidazole bis trifluoromethyl salt, quality 0.25g.
Test condition is same as Example 1, is tested under humidified condition with pure gas, CO2Infiltration coefficient is 633barrer
(1barrer=10-10cm3(STP)cm/(cm2S cmHg)), CO2/N2Separation factor is 29, CO2/CH4Separation factor is 24.
Comparative example 1, a kind of preparation of hybridized film, preparation process is: it is total to weigh 0.5g polyoxyethylene-polycaprolactam block
Polymers (trade name Pebax 1657), 7g dehydrated alcohol and 3g deionized water are added in the three-necked flask with condenser pipe, 80
DEG C water bath with thermostatic control in, with the speed return stirring 2h of 500r/min, make polyoxyethylene therein-polycaprolactam block copolymerization
Object all dissolves, and obtains casting solution, and clean polytetrafluoroethylene (PTFE) culture dish (Φ will be poured into after obtained casting solution standing and defoaming
In 100mm), for 24 hours, then drying for 24 hours, obtains about 100 μm of hybridized films of thickness under 45 DEG C, vacuum condition for drying at room temperature.
Test condition is same as Example 1, is tested under humidified condition with pure gas, CO2Infiltration coefficient is 460barrer
(1barrer=10-10cm3(STP)cm/(cm2S cmHg)), CO2/N2Separation factor is 22, CO2/CH4Separation factor is 18.
To sum up, in preparation process of the present invention, the ionic liquid of 1- butyl -2,3- methylimidazole hexafluorophosphate preparation is selected
The CO of body2Infiltration coefficient and CO2/N2, CO2/CH4Separation factor highest.With the increase of imidazole type ion liquid additive amount, CO2It seeps
Saturating coefficient and CO2/N2, CO2/CH4Separation factor all increases with it.
Although invention has been described above, but the invention is not limited in above-mentioned embodiment, on
The specific embodiment stated is only schematical, rather than restrictive, and those skilled in the art are of the invention
Under enlightenment, without deviating from the spirit of the invention, many variations can also be made, these belong to protection of the invention it
It is interior.
Claims (4)
1. a kind of ionic liquid blend film, which is characterized in that main component be polyoxyethylene-polycaprolactam block copolymer with
And imidazole type ion liquid；Wherein, imidazole type ion liquid accounts for polyoxyethylene-polycaprolactam block copolymer mass fraction
For 5-50%.
2. ionic liquid blend film as described in claim 1, which is characterized in that the imidazole type ion liquid is 1- butyl-
2,3- methylimidazole hexafluorophosphates, -3 methyl imidazolium tetrafluoroborate of 1- butyl, -3 methylimidazole dicyan amine salt of 1- butyl,
Any ionic liquid at room temperature containing imidazoles in 1- ethyl-3-methylimidazole bis trifluoromethyl salt.
3. a kind of method for preparing ionic liquid blend film as claimed in claim 1 or 2, which comprises the following steps:
Step 1: polyoxyethylene-polycaprolactam the block for being 55-60% by the polyoxyethylene segment mass fraction of certain mass
Copolymer is added in the ethanol solution that mass fraction is 65-75%, is heated at reflux to 75~90 DEG C, makes polyoxyethylene-therein
Polycaprolactam block copolymer is completely dissolved, and is cooled to room temperature, and the polyoxyethylene-that mass fraction is 2-7% is made and gathers in oneself
Amide block copolymers solution；
Step 2: taking polyoxyethylene-polycaprolactam block copolymer solution of certain mass, it is added dropwise to imidazole type ion liquid
Mixed solution A is made, wherein the imidazole type ion liquid accounts for polyoxyethylene-polycaprolactam block copolymer quality point
Number is 5-50%, and magnetic agitation is completely dissolved imidazole type ion liquid therein, is cooled to room temperature obtained casting solution；
Step 3: casting solution made from step 2 is added in polytetrafluoroethylene (PTFE) culture dish, film-forming at room temperature, in 35-60
Dry 24~48h is under DEG C vacuum condition to get ionic liquid blend film.
4. the application for the ionic liquid blend film that the method for preparing ionic liquid blend film as claimed in claim 3 obtains, special
Sign is, is used for CO2/CH4Or CO2/N2Separation.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107694353A (en) * | 2017-09-05 | 2018-02-16 | 齐齐哈尔大学 | The preparation method of ethyl cellulose and ionic liquid gas separation membrane |
| CN111467933B (en) * | 2019-01-23 | 2021-09-07 | 中国科学院过程工程研究所 | Method for selectively separating ammonia gas by multi-site proton type ionic liquid composite membrane |
| CN111804161B (en) * | 2019-04-12 | 2022-05-17 | 天津工业大学 | For CO2Separated amino acid ion liquid coated nano microsphere/polymer hybrid membrane |
| CN110141977A (en) * | 2019-06-17 | 2019-08-20 | 沈阳工业大学 | Graft type ionic liquid polyimide film and preparation method and applications |
| CN112973468B (en) * | 2019-12-14 | 2022-04-08 | 中国科学院大连化学物理研究所 | Method for preparing two-dimensional covalent organic framework ultrathin nanosheet material composite membrane and application |
| CN114425246B (en) * | 2020-09-28 | 2023-04-11 | 中国石油化工股份有限公司 | Ionic liquid supported composite membrane and preparation method and application thereof |
| CN113457469B (en) * | 2021-08-04 | 2022-08-16 | 中国矿业大学 | High-temperature-resistant PDMS/ionic liquid composite membrane and preparation method and application thereof |
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| CN103521100A (en) * | 2013-10-29 | 2014-01-22 | 天津大学 | High-molecular-functional mesoporous silica hybrid membrane, preparation method and applications |
| CN103894081A (en) * | 2014-03-21 | 2014-07-02 | 天津大学 | Cross-linked polyoxyethylene-polycaprolactam block copolymer film as well as preparation and application thereof |
| CN104741009A (en) * | 2015-03-20 | 2015-07-01 | 江苏大学 | Preparation method of salicylic acid molecular imprinted cellulose acetate blended membrane and application of blended membrane |
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| KR101149079B1 (en) * | 2010-01-18 | 2012-05-24 | 한국에너지기술연구원 | Enhanced gas transport ionic liquid-polymer gel membrane and methods of producing same |
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| CN103521100A (en) * | 2013-10-29 | 2014-01-22 | 天津大学 | High-molecular-functional mesoporous silica hybrid membrane, preparation method and applications |
| CN103894081A (en) * | 2014-03-21 | 2014-07-02 | 天津大学 | Cross-linked polyoxyethylene-polycaprolactam block copolymer film as well as preparation and application thereof |
| CN104741009A (en) * | 2015-03-20 | 2015-07-01 | 江苏大学 | Preparation method of salicylic acid molecular imprinted cellulose acetate blended membrane and application of blended membrane |
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