CN104971628A - Multilayer gas separation composite membrane and preparation method thereof - Google Patents
Multilayer gas separation composite membrane and preparation method thereof Download PDFInfo
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- CN104971628A CN104971628A CN201410146013.XA CN201410146013A CN104971628A CN 104971628 A CN104971628 A CN 104971628A CN 201410146013 A CN201410146013 A CN 201410146013A CN 104971628 A CN104971628 A CN 104971628A
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Abstract
The invention aims to improve the gas separation performance of a membrane material by means of blending modification to the membrane material and particularly provides a multilayer gas separation composite membrane having an ultrathin separation layer and a preparation method thereof. The membrane is mainly used for separating acidic gases, such as CO2 and the like. In the invention, the multilayer gas separation composite membrane is prepared with a block polymer Pebax and glycerol triacetate as the main material of a separation layer. The preparation method is simple and is easy to achieve large-scale production.
Description
Technical field
The present invention relates to composite gas separation, specifically provide a kind of polyether-b-polyamide and triacetyl glycerine multi-layer gas composite membrane for separation and preparation method thereof.
Background technology
CO
2recycling become the focus of global concern.The CO of latest developments
2trapping and Plugging Technology Applied are at present by indispensable part in the reduction of greenhouse gas discharge capital project extensively approved.Wherein CO
2trapping shared by energy consumption maximum, be the bottleneck of this technical development.
Gas separation membrane is a kind of new technology of development in recent years.It is separated by the difference of the infiltration rate of film according to gas with various, is widely used in air separation, CO
2remove, the field such as dehumidification of gas and hydrogen recovery.The membrane material of function admirable is the key of gas film development, and the preparation of composite membrane is then the industrialized important step of membrane technology.
Business-like block copolymer Pebax be to Freeman find to CO
2there is a kind of macromolecule member material after the PEO polymer modification of compatibility.Its structural formula is as follows:
Wherein PA rigid chain segment is nylon 6 (PA6) or nylon 12 (PA12), provides mechanical strength; PE soft segment is PEO (PEO) or polybutylene oxide (PTMO), provides gas passage.Multiple Type can be divided into according to PA, PE contamination difference.Due to the ether-oxygen bond in molecule and CO
2molecule has corner dipole moment effect, and Pebax is for CO
2have higher selective, the advantage such as its good film-forming property, acid and alkali-resistance, heat endurance and good mechanical stability becomes the focus of recent researches simultaneously.
As a kind of rubbery state macromolecular material, it is the industrialized key of membrane technology that preparation has ultra-thin flawless composite membrane.Utilized dip coating to prepare PEI/PDMS/Pebax1657/PDMS composite membrane, its CO such as Ren
2permeation flux is 157GPU, CO
2/ N
2separation is 64.
In order to improve the separating property of membrane material further, modification to be carried out to it.Blending and modifying is exactly a kind of important method.This method of modifying regulates membrane structure, controlling diaphragm performance by the difference of Compatibility Between Polymers.Simply, without chemical action, reproducible, polymer blend stock blend advantage separately can be utilized.Feng etc. prepare homogeneous membrane with small-molecule substance GTA and Pebax is blended, found that the infiltration coefficient of gas in film significantly improves when GTA concentration exceedes certain limit, CO
2infiltration coefficient can reach 974GPU, CO
2/ N
2separation is 52.
The industrial main method preparing composite gas separation is dip-coating method at present.This method is easy to prepare the gas separation membrane with ultra-thin parting absciss layer, improves the gas permeability of film.But because counterdie is perforated membrane, easily occur that phenomenon is oozed in hole, be difficult to form zero defect selective separating on film surface.The present invention adopts the membrane material with high gas permeability, as polydimethylsiloxane carries out plug-hole as intermediate layer material to open support counterdie, effectively can prevent hole from oozing phenomenon and occur; Block polymer Pebax and triacetyl glycerine is adopted to have multi-layer gas composite membrane for separation, the CO of this film as separation layer materials preparation
2permeation flux can reach 424GPU, CO
2/ N
2separation is 41.3.
The invention provides a kind of composite gas separation membrane with ultra-thin parting absciss layer, this film has higher CO
2permeation flux, and film-forming method is simple, is easy to large-scale production.
Summary of the invention
The object of the invention is to carry out blending and modifying to improve the gas separating property of membrane material to membrane material, specifically provide a kind of polyether-b-polyamide and triacetyl glycerine multi-layer gas composite membrane for separation and preparation method thereof.The present invention adopts business-like block polymer Pebax and triacetyl glycerine (GTA) to prepare multi-layer gas composite membrane for separation as the main membrane material of separating layer, is mainly used in CO
2deng the separation of sour gas.
For achieving the above object, the technical scheme that the present invention is used is:
A kind of multi-layer gas composite membrane for separation, it is characterized in that, described structure of composite membrane comprises (structural representation of multilayer complex films is shown in Fig. 1):
Counterdie, has loose structure;
Intermediate layer, has the membrane material of gas permeability, is arranged on counterdie;
Separating layer, polyether-b-polyamide (Pebax) and triacetyl glycerine (GTA) blend solution coating, coating is on the intermediate layer;
Protective layer, is arranged in separating layer.
Counterdie of the present invention is perforated membrane, preferred PS membrane, and intermediate layer and protective layer are made up of the membrane material of high gas permeability, and as rubbery state compound, preferred material is dimethyl silicone polymer.The two can select same material, also can adopt different materials.
PDMS carries out plug-hole as intermediate layer material to open support counterdie, effectively can prevent hole from oozing phenomenon and occur.When PDMS surface coating Pebax-GTA blend solution, because PDMS surface energy is less, easily there is defect in coating, and PDMS silicon rubber can be adopted to carry out restoration and protection to Pebax-GTA separating layer.
Multi-layer gas composite membrane for separation of the present invention, is characterized in that: in separating layer, and in described polyether-b-polyamide and triacetyl glycerine blend solution, the mass ratio of polyether-b-polyamide and triacetyl glycerine is 95:5 ~ 5:95.
Multi-layer gas composite membrane for separation of the present invention, is characterized in that: separating layer thickness is at 1 ~ 10 μm.
Present invention also offers the preparation method of described multi-layer gas composite membrane for separation, it is characterized in that, comprise the steps:
(1), polyether-b-polyamide and triacetyl glycerine are dissolved in organic solvent, are coated in PDMS interlayer surfaces after standing and defoaming, after desolventizing, obtain separating layer;
(2) by mass percent be 0.1% ~ 10% dimethyl silicone polymer solution be coated in separating layer surface, obtain multi-layer gas composite membrane for separation after solidification.
The preparation method of multi-layer gas composite membrane for separation of the present invention, is characterized in that: the mass ratio of polyether-b-polyamide and organic solvent is 0.1:99.9 ~ 10:90; Wherein organic solvent is n-butanol, dimethylacetylamide.
The preparation method of multi-layer gas composite membrane for separation of the present invention, its preferred preparation process is as follows:
(1), the preparation of separating layer coating solution: the Pebax solution adding polyether-b-polyamide configuration certain mass concentration in n-butanol, the triacetyl glycerine of certain mass ratio is added wherein after stirring, add thermal agitation and obtain transparent and homogeneous solution, standing and defoaming; Wherein the mass ratio of polyether-b-polyamide and n-butanol is 0.1:99.9 ~ 10:90, and the mass ratio of polyether-b-polyamide and triacetyl glycerine is 95:5 ~ 5:95;
(2), with dip-coating method at PSF/PDMS composite membrane PDMS surface coating separating layer coating solution, PSF/PDMS/Pebax-GTA composite membrane after desolventizing, is obtained;
(3), by mass percent be the Pebax-GTA separating layer surface being coated in PSF/PDMS/Pebax-GTA composite membrane after the dimethyl silicone polymer solution left standstill deaeration of 0.1% ~ 10%, after desolvation, finally obtain PSF/PDMS/Pebax-GTA/PDMS multilayer complex films.
Advantage of the present invention is as follows:
1, the present invention adopts triacetyl glycerine (GTA) to carry out blending and modifying to Pebax membrane material, to increase in separating layer can with CO
2interactional functional group, improves the permeation flux of gas in composite membrane greatly.
2, the multi-layer gas composite membrane for separation that prepared by the present invention effectively inhibits coating procedure mesopore to ooze the generation of phenomenon due to the existence of intermediate layer PDMS layer, can obtain the composite membrane with ultra-thin parting absciss layer; Adopt again PDMS to protect separating layer surface, ensure the gas separating property of polyether-b-polyamide and triacetyl glycerine multi-layer gas composite membrane for separation.
3, film-forming method is simply easy to operation, and industrial prospect is good.
Accompanying drawing explanation
Fig. 1 is multi-layer film structure schematic diagram of the present invention, wherein: (1), counterdie; (2), intermediate layer; (3), separating layer; (4), protective layer.
The gas test installation drawing of Fig. 2 composite gas separation, wherein: (5), gas cylinder; (6), pressure-reducing valve; (7), valve; (8), Pressure gauge; (9), pond is evaluated; (11), soap bubble flowmeter; (12), temperature control baking oven.
Detailed description of the invention
The present invention adopts the composite membrane test system shown in accompanying drawing 2.For the test of pure gas, first regulate the temperature that temperature control baking oven 12 makes evaluation pond 9 keep certain, valve-off 7, regulate the pressure that pressure-reducing valve 6 makes feed side keep certain, per-meate side leads to air.Soap bubble flowmeter 11 is used to measure the gas flow rate of per-meate side, and by the permeation flux of formulae discovery gas below in film and separation.
In formula:
Flux GPU1GPU=7.5 × 10 of J---gas
-12m
3/ (m
2sPa)
Δ p---be both sides differential pressure of membrane, Pa
Q---be volumetric flow of gas, m
3s
-1
A---be effective film area, m
2
α---gas system separation
Below in conjunction with embodiment in detail the present invention is described in detail.
Embodiment 1
Respectively prepare 1% and 3% mass concentration Pebax1074 (Pebax1074, model:
1074, French Arkema company) butanol solution, add thermal agitation and obtain transparent and homogeneous solution.The method adopting dip coating to be combined with wet coating method after placing deaeration, at polysulfone porous membrane surface coating coatings liquid, obtains PSF/Pebax1074 composite membrane after desolventizing.The separating property of test membrane, experimental result lists in table 1.
The experimental result of table 1 embodiment 1
Embodiment 2
Prepare the Pebax1074 butanol solution of 1% and 3% mass concentration respectively, add thermal agitation and obtain transparent and homogeneous solution.Adopt dip coating at the PDMS surface coating coatings liquid of composite membrane PSF/PDMS after placing deaeration, after desolventizing, obtain PSF/PDMS/Pebax1074 composite membrane.The separating property of test membrane, experimental result lists in table 2.
The experimental result of table 2 embodiment 2
Embodiment 3
Prepare the Pebax1074 butanol solution of 1% mass concentration, add the GTA of different quality after heating stirs, continue to add the Pebax1074-GTA coating solution that thermal agitation obtains different quality specific concentration.Adopt dip-coating method at the PDMS surface coating of PSF/PDMS composite membrane after standing and defoaming, after desolvation, obtain PSF/PDMS/Pebax1074-GTA multilayer complex films.The separating property of test membrane, experimental result lists in table 3.
The experimental result of table 3 embodiment 3
Embodiment 4
Prepare the pentane solution of the dimethyl silicone polymer of 1% mass concentration, stirring and dissolving after deaeration, be coated on the separating layer surface of the multilayer complex films PSF/PDMS/Pebax1074-GTA (GTA mass concentration is 60%) of embodiment 3 gained, after deviating from solvent, obtain PSF/PDMS/Pebax1074-GTA/PDMS multilayer complex films.Test the gas separating property of multilayer complex films, experimental result lists in table 4.
The experimental result of table 4 embodiment 4
Embodiment 1 and embodiment 2 all select the Pebax1074 concentration of 1% and 3% mass concentration to prepare composite membrane, as can be seen from the data of table 1 respectively, the Pebax solution of 1% obviously occurs that in coating procedure phenomenon is oozed in hole, when Pebax mass concentration increases to 3%, hole is oozed phenomenon and is improved, but along with the increase of Pebax mass concentration, gas increases at film inner transmission matter resistance, gas permeation flux reduces, and also can draw similar conclusion from table 2 data.
Embodiment 1 prepare PSF/Pebax1074 film and embodiment 2 in preparation PSF/PDMS/Pebax1074 composite membrane gas permeation data compare, can see that Pebax coating solution is effectively sprawled on PDMS surface, intermediate layer, hole is oozed phenomenon and is inhibited, and can form thinner selective separating simultaneously.
PSF/PDMS/Pebax1074-GTA composite membrane prepared by embodiment 3, the permeation flux making gas in composite membrane that adds of GTA material enlarges markedly as can be seen from Table 3, and adding of GTA is described, increases CO
2absorption property in film; the PSF/PDMS/Pebax1074-GTA composite membrane of comparing embodiment 3 and the PSF/PDMS/Pebax1074-GTA/PDMS composite membrane of embodiment 4; as can be seen from the data of table 4, PDMS protective layer effectively reduces the impact of separating layer defect on gas separating property.
The composite membrane of embodiment 4 and embodiment 1, embodiment 2 compares, can find out with GTA blending and modifying after, in the multi-layer gas composite membrane for separation utilizing Pebax1074-GTA solution to prepare, gas permeation flux is significantly increased, and gas separating property is constant.
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to Spirit Essence of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (10)
1. a multi-layer gas composite membrane for separation, is characterized in that, described structure of composite membrane comprises:
Counterdie, has loose structure;
Intermediate layer, has the membrane material of gas permeability, is arranged on counterdie;
Separating layer, polyether-b-polyamide and triacetyl glycerine blend solution coating, coating is on the intermediate layer;
Protective layer, is arranged in separating layer.
2. according to multi-layer gas composite membrane for separation described in claim 1, it is characterized in that: described counterdie is PS membrane.
3. according to multi-layer gas composite membrane for separation described in claim 1, it is characterized in that: described intermediate layer and protective layer are made up of rubbery state compound.
4. according to multi-layer gas composite membrane for separation described in claim 1 or 3, it is characterized in that: described intermediate layer and protective layer are made up of dimethyl silicone polymer.
5. according to multi-layer gas composite membrane for separation described in claim 1, it is characterized in that: in separating layer, in described polyether-b-polyamide and triacetyl glycerine blend solution, the mass ratio of polyether-b-polyamide and triacetyl glycerine is 95:5 ~ 5:95.
6., according to the arbitrary described multi-layer gas composite membrane for separation of Claims 1 to 5, it is characterized in that: separating layer thickness is at 1 ~ 10 μm.
7., according to a preparation method for multi-layer gas composite membrane for separation described in claim 1, it is characterized in that, comprise the steps:
(1), polyether-b-polyamide and triacetyl glycerine are dissolved in organic solvent, are coated in PDMS interlayer surfaces after standing and defoaming, after desolventizing, obtain separating layer;
(2) by mass percent be 0.1% ~ 10% dimethyl silicone polymer solution be coated in separating layer surface, obtain multi-layer gas composite membrane for separation after solidification.
8. according to the preparation method of multi-layer gas composite membrane for separation described in claim 7, it is characterized in that: the mass ratio of polyether-b-polyamide and organic solvent is 0.1:99.9 ~ 10:90; Wherein organic solvent is n-butanol, dimethylacetylamide.
9. according to the preparation method of multi-layer gas composite membrane for separation described in claim 7 or 8, it is characterized in that, concrete preparation process is as follows:
(1), the preparation of separating layer coating solution: the Pebax solution adding polyether-b-polyamide configuration certain mass concentration in n-butanol, the triacetyl glycerine of certain mass ratio is added wherein after stirring, add thermal agitation and obtain transparent and homogeneous solution, standing and defoaming; Wherein the mass ratio of polyether-b-polyamide and n-butanol is 0.1:99.9 ~ 10:90, and the mass ratio of polyether-b-polyamide and triacetyl glycerine is 95:5 ~ 5:95;
(2), with dip-coating method at PSF/PDMS composite membrane PDMS surface coating separating layer coating solution, PSF/PDMS/Pebax-GTA composite membrane after desolventizing, is obtained;
(3), by mass percent be the Pebax-GTA separating layer surface being coated in PSF/PDMS/Pebax-GTA composite membrane after the dimethyl silicone polymer solution left standstill deaeration of 0.1% ~ 10%, after desolvation, finally obtain PSF/PDMS/Pebax-GTA/PDMS multilayer complex films.
10. described in a claim 1, multi-layer gas composite membrane for separation is applied in the separation field of sour gas.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105964152A (en) * | 2016-05-13 | 2016-09-28 | 天津工业大学 | Preparation for Pebax double-layer flat sheet composite membrane |
| CN108883378A (en) * | 2016-04-04 | 2018-11-23 | 住友化学株式会社 | Sour gas seperation film and the sour gas separation method and sour gas separation module and sour gas separator for having used it |
| CN112403839A (en) * | 2020-11-30 | 2021-02-26 | 天津大学 | Large-scale preparation method and device of carbon dioxide separation multilayer composite membrane |
Citations (2)
| 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 |
| CN103506017A (en) * | 2012-06-27 | 2014-01-15 | 中国科学院大连化学物理研究所 | Polyether-b-polyamide and glycerol triacetate blend membrane as well as preparation method and application thereof |
-
2014
- 2014-04-11 CN CN201410146013.XA patent/CN104971628A/en active Pending
Patent Citations (2)
| 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 |
| CN103506017A (en) * | 2012-06-27 | 2014-01-15 | 中国科学院大连化学物理研究所 | Polyether-b-polyamide and glycerol triacetate blend membrane as well as preparation method and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108883378A (en) * | 2016-04-04 | 2018-11-23 | 住友化学株式会社 | Sour gas seperation film and the sour gas separation method and sour gas separation module and sour gas separator for having used it |
| CN108883378B (en) * | 2016-04-04 | 2021-08-24 | 住友化学株式会社 | Acid gas separation membrane, acid gas separation method using same, acid gas separation module, and acid gas separation device |
| CN105964152A (en) * | 2016-05-13 | 2016-09-28 | 天津工业大学 | Preparation for Pebax double-layer flat sheet composite membrane |
| CN112403839A (en) * | 2020-11-30 | 2021-02-26 | 天津大学 | Large-scale preparation method and device of carbon dioxide separation multilayer composite membrane |
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