CN101596412A - Be used for strengthened polyethylene imine fixed carrier composite membrane of separating acid gas and preparation method thereof - Google Patents
Be used for strengthened polyethylene imine fixed carrier composite membrane of separating acid gas and preparation method thereof Download PDFInfo
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- CN101596412A CN101596412A CNA2009100693146A CN200910069314A CN101596412A CN 101596412 A CN101596412 A CN 101596412A CN A2009100693146 A CNA2009100693146 A CN A2009100693146A CN 200910069314 A CN200910069314 A CN 200910069314A CN 101596412 A CN101596412 A CN 101596412A
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- polyvinylamine
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- ethylenediamine
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Abstract
The present invention relates to a kind of strengthened polyethylene imine fixed carrier composite membrane that is used for separating acid gas and preparation method thereof.With polysulfones or poly (ether-sulfone) ultrafiltration membrane is basement membrane, and it is carried out preliminary treatment; The polyvinylamine aqueous solution is mixed with polyaniline nano fiber aqueous dispersions, gas phase nano silica aqueous dispersion and ethylenediamine solution respectively, be mixed with casting solution, utilize coating device that casting solution is coated on the basement membrane; Drying obtains polyvinylamine-polyaniline nano fiber composite membrane, polyvinylamine-gas phase nano silica composite membrane and the polyvinylamine-ethylenediamine composite membrane of separating acid gas respectively.This procedure is simple, fixed carrier composite membrane filming performance and having good stability, and its major parameter is: CO
2Infiltration rate can reach 150 * 10
-6Cm
3(STP)/cm
2.s.cmHg, CO
2/ CH
4(volume ratio 10: 90), CO
2/ N
2(volume ratio 20: 80) best result can reach 220,110 respectively from the factor.
Description
Technical field
The present invention relates to a kind of strengthened polyethylene imine fixed carrier composite membrane that is used for separating acid gas and preparation method thereof.
Background technology
Fixed carrier composite membrane is a kind of novel gas separation membrane, has high osmosis and high selectivity.Carrier is transmitted in the promotion that amino can be used as in the composite membrane, polyvinylamine because contain a large amount of high activity primary amino radicals can with CO
2Reversible reaction takes place, and is a kind of desirable separation of C O therefore
2The immobilization carrier membrane material.
With polyvinylamine (PVAm) is that separating layer, polysulfones (PS) or polyether sulfone (PES) are that PVAm/PS or the PVAm/PES composite membrane that supporting layer prepares has more excellent CO
2See through separating property, yet will realize the large-scale application of PVAm composite membrane, further improving it, to see through separating property very necessary.Membrane material has material impact to the performance of composite membrane, and introducing nano material or volatile small molecule amine have the potentiality of preparing high osmosis high selectivity film in composite membrane.Nano material has certain microcosmic controllability to polymeric material, and has fundamental propertys such as small-size effect, skin effect, and these nanoparticulate dispersed in high-molecular organic material, be can be made into the nano combined gas separation membrane with excellent properties.Nano material generally can be divided into organic nano material and inorganic nano material two classes, organic nano material has more functional group and some special chemical constitution, combine better with polymeric matrix, and inorganic nano material itself has very strong sieving capacity to gas molecule, therefore, organic or inorganic nano particle and the even blend of macromolecular material can be prepared have the high composite membrane that sees through separating property.In addition, some volatile small molecule amine classes such as ethylenediamine, triethylamine etc. have stronger locomotivity, it is crosslinked that hydrogen bond takes place in primary amino radical group in energy and the polyvinylamine, and the carrier that the amino of these small molecule amine classes can be used as in promoting to transmit equally uses, therefore be introduced into the stability that has at first improved film in the fixed carrier composite membrane by crosslinked action, next has increased amount vector in the film, strengthened the locomotivity of carrier in the film at last, these all help improving the separating property that sees through of fixed carrier composite membrane.
Therefore, can be by in the immobilization carrier film, introducing the see through separating property of some new materials with reinforced composite membrane with excellent properties.
Summary of the invention
The object of the present invention is to provide a kind of strengthened polyethylene imine fixed carrier composite membrane that is used for separating acid gas and preparation method thereof.This fixed carrier composite membrane filming performance and having good stability has higher separation factor and excellent permeation performance simultaneously, and preparation method's operating process is simple.
The strengthened polyethylene imine fixed carrier composite membrane that is used for separating acid gas provided by the invention is
With polysulfones or poly (ether-sulfone) ultrafiltration membrane be basement membrane and be selected from polyvinylamine and polyaniline nano fiber, polyvinylamine and gas phase nano silica or polyvinylamine and ethylenediamine to mix the composition casting solution be feedstock production, according to mass ratio:
The mass ratio of polyvinylamine and polyaniline nano fiber is 1～10: 1;
The mass ratio of polyvinylamine and gas phase nano silica is 1～10: 1;
Polyvinylamine and ethylenediamine mass ratio are 1: 0～9;
Concrete processing step: the casting film aqueous solution or the aqueous dispersions that prepare are coated on through being soaked on the polysulfones of handling in the aqueous solution or the aqueous slkali or poly (ether-sulfone) ultrafiltration membrane basement membrane air dry under the room temperature.
The wet coating layer thickness of described composite membrane is 300-400 μ m.
The strengthened polyethylene imine fixed carrier composite membrane major parameter that is used for separating acid gas provided by the invention: to CO
2/ CH
4The selection through performance of gaseous mixture (volume ratio 10: 90) is: CO
2/ CH
4Separation factor 40～220, CO
2Infiltration rate (10～100) * 10
-6Cm
3(STP) cm
-2s
-1CmHg
-1To CO
2/ N
2The selection through performance of gaseous mixture (volume ratio 20: 80) is: CO
2/ N
2Separation factor 75～110, CO
2Infiltration rate (60～150) * 10
-6Cm
3(STP) cm
-2s
-1MHg
-1
The step that the preparation method who is used for the strengthened polyethylene imine fixed carrier composite membrane of separating acid gas provided by the invention comprises:
1) polysulfones of nominal molecular cut off 6000～30000 or poly (ether-sulfone) ultrafiltration membrane being dipped in deionized water solution, mass concentration as basement membrane is that 1～10% aqueous sodium carbonate or volumetric concentration are in 1～10% the ethylenediamine solution, at room temperature soak more than the 24h, standby.
2) be that 1～3% the polyvinylamine aqueous solution and mass fraction are 1～3% polyaniline nano fiber aqueous dispersions with mass fraction, blend makes casting solution;
Or be that 1～3% the polyvinylamine aqueous solution and mass fraction are 1～3% gas phase nano silica aqueous dispersion with mass fraction, blend makes casting solution;
Or be that 1～3% the polyvinylamine aqueous solution and ethylenediamine solution blend make casting solution with mass fraction.
3) utilize general coating device, with step 2) casting solution that makes is coated on the membrane surface of handling through step 1), in temperature is 25～35 ℃, 30～40% times dryings of relative humidity obtain polyvinylamine-polyaniline nano fiber composite membrane, polyvinylamine-gas phase nano silica composite membrane or the polyvinylamine-ethylenediamine composite membrane of separating acid gas respectively.
Specifeca tion speeification of the present invention is: CO
2Infiltration rate can reach 150 * 10
-6Cm
3(STP)/cm
2.s.cmHg, CO-
2/ CH
4(volume ratio 10: 90), CO
2/ N
2(volume ratio 20: 80) best result can reach 220,110 respectively from the factor.Film-forming process is simple, with polyvinylamine and organic nano material (as polyaniline nano fiber), inorganic nano material (as gas phase nano silica) or volatile small molecule amine class (as ethylenediamine) by after the solution blended process blend, utilize coating device can prepare corresponding composite membrane, adding nano material or small molecule amine can bring a lot of new character to composite membrane, has improved the selection through performance of polyethylene imine fixed carrier composite membrane to sour gas.
Description of drawings
Polyvinylamine-polyaniline nano fiber that Fig. 1 obtains for embodiment 1/polysulfone composite membrane surface texture sem photograph.
Polyvinylamine-polyaniline nano fiber that Fig. 2 obtains for embodiment 1/polysulfone composite membrane section structure sem photograph.
The specific embodiment
Embodiment 1
Make mass concentration and be 3% the polyvinylamine aqueous solution, make mass concentration simultaneously and be 2% polyaniline nano fiber aqueous dispersions, according to the polyvinylamine aqueous solution and polyaniline nano fiber aqueous dispersions mass ratio preparation in 5: 1 casting solution.It is 5% ethylenediamine solution that polysulfones flat plate ultrafiltration membrane (the nominal molecular cut off is 6000) is dipped in volumetric concentration, at room temperature soaks more than the 24h, and dry back is standby.Utilizing the wet coating layer thickness of coating device control composite membrane is 350 μ m, the casting solution of above-mentioned preparation is coated on the polysulfones flat plate ultrafiltration membrane after the processing, in temperature is 30 ℃, and 40% time drying of relative humidity obtains polyvinylamine-polyaniline nano fiber/polysulfone composite membrane.Use CO
2/ CH
4Gaseous mixture (volume ratio 10: 90) carries out performance test to it.Test result: when feed gas pressure be 83.5～1801.4cmHg (0.1～2.4MPa) time, CO
2/ CH
4Separation factor 215～40, CO
2Infiltration rate (50～10) * 10
-6Cm
3(STP) cm
-2s
-1CmHg
-1
Embodiment 2
Make mass concentration and be 2% the polyvinylamine aqueous solution, make mass concentration simultaneously and be 2% gas phase nano silica aqueous dispersion, according to the polyvinylamine aqueous solution and gas phase nano silica aqueous dispersion mass ratio preparation in 3: 1 casting solution.It is 1% aqueous sodium carbonate that polysulfones flat plate ultrafiltration membrane (the nominal molecular cut off is 6000) is dipped in mass concentration, at room temperature soaks more than the 24h, and dry back is standby.Utilizing the wet coating layer thickness of coating device control composite membrane is 400 μ m, the casting solution of above-mentioned preparation is coated on the polysulfones flat plate ultrafiltration membrane after the processing, in temperature is 30 ℃, and 40% time drying of relative humidity obtains polyvinylamine-gas phase nano silica/polysulfone composite membrane.Use CO
2/ CH
4Gaseous mixture (volume ratio 10: 90) carries out performance test to it.Test result: when feed gas pressure be 83.5～1576.4cmHg (0.1～2MPa) time, CO
2/ CH
4Separation factor 130～60, CO
2Infiltration rate (100～40) * 10
-6Cm
3(STP) cm
-2s
-1CmHg
-1
Embodiment 3
Make mass concentration and be 3% the polyvinylamine aqueous solution.Polysulfones flat plate ultrafiltration membrane (the nominal molecular cut off is 6000) is dipped in deionized water solution, at room temperature soaks more than the 24h, dry back is standby.Utilizing the wet coating layer thickness of coating device control composite membrane is 300 μ m, the casting solution of above-mentioned preparation is coated on the polysulfones flat plate ultrafiltration membrane after the processing, and be 30 ℃ in temperature, 40% time drying of relative humidity obtains polyvinylamine/polysulfone composite membrane.Use CO
2/ N
2Gaseous mixture (volume ratio 20: 80) carries out performance test to it.Test result: when feed gas pressure be 113.5～1118.8cmHg (0.15～1.5MPa) time, CO
2/ N
2Separation factor 60～12, CO
2Infiltration rate (120～45) * 10
-6Cm
3(STP) cm
-2s
-1CmHg
-1
Embodiment 4
Make mass concentration and be 3% the polyvinylamine aqueous solution, according to polyvinylamine and ethylenediamine mass ratio preparation in 1: 5 casting solution.Polysulfones flat plate ultrafiltration membrane (the nominal molecular cut off is 6000) is dipped in deionized water solution, at room temperature soaks more than the 24h, dry back is standby.Utilizing the wet coating layer thickness of coating device control composite membrane is 300 μ m, the casting solution of above-mentioned preparation is coated on the polysulfones flat plate ultrafiltration membrane after the processing, and be 30 ℃ in temperature, 40% time drying of relative humidity obtains polyvinylamine-ethylenediamine/polysulfone composite membrane.Use CO
2/ N
2Gaseous mixture (volume ratio 20: 80) carries out performance test to it.Test result: when feed gas pressure be 83.5～1126.3cmHg (0.1～1.5MPa) time, CO
2/ N
2Separation factor 100～75, CO
2Infiltration rate (150～60) * 10
-6Cm
3(STP) cm
-2s
-1CmHg
-1
Claims (4)
1, a kind of strengthened polyethylene imine fixed carrier composite membrane that is used for separating acid gas, it is characterized in that it be with polysulfones or poly (ether-sulfone) ultrafiltration membrane be basement membrane and be selected from polyvinylamine and polyaniline nano fiber, polyvinylamine and gas phase nano silica or polyvinylamine and ethylenediamine to mix the composition casting solution be feedstock production, casting solution is according to proportioning:
The mass ratio of polyvinylamine and polyaniline nano fiber is 1～10: 1;
The mass ratio of polyvinylamine and gas phase nano silica is 1～10: 1;
Polyvinylamine and ethylenediamine mass ratio are 1: 0～9;
Concrete processing step: the casting film aqueous solution or the aqueous dispersions that prepare are coated on through being soaked on the polysulfones of handling in the aqueous solution or the aqueous slkali or poly (ether-sulfone) ultrafiltration membrane basement membrane air dry under the room temperature.
2,, it is characterized in that the wet coating layer thickness of this composite membrane is 300-400 μ m by the described composite membrane of claim 1.
3, by claim 1 or 2 described composite membranes, it is characterized in that this composite membrane major parameter:
To 10: 90 CO of volume ratio
2/ CH
4Gaseous mixture selects through performance to be: CO
2/ CH
4Separation factor 40～220, CO
2Infiltration rate (10～100) * 10
-6Cm
3(STP) cm
-2s
-1CmHg
-1
To 20: 80 CO of volume ratio
2/ N
2Gaseous mixture selects through performance to be: CO
2/ N
2Separation factor 75～110, CO
2Infiltration rate (60～150) * 10
-6Cm
3(STP) cm
-2s
-1CmHg
-1
4, claim 1 or the 2 described preparation methods that are used for the strengthened polyethylene imine fixed carrier composite membrane of separating acid gas is characterized in that the step that comprises:
1) polysulfones of nominal molecular cut off 6000～30000 or poly (ether-sulfone) ultrafiltration membrane being dipped in deionized water solution, mass concentration as basement membrane is that 1～10% aqueous sodium carbonate or volumetric concentration are in 1～10% the ethylenediamine solution, at room temperature soak more than the 24h, standby;
2) be that 1～3% the polyvinylamine aqueous solution and mass fraction are 1～3% polyaniline nano fiber aqueous dispersions with mass fraction, blend makes casting solution;
Or be that 1～3% the polyvinylamine aqueous solution and mass fraction are 1～3% gas phase nano silica aqueous dispersion with mass fraction, blend makes casting solution;
Or be that 1～3% the polyvinylamine aqueous solution and ethylenediamine solution blend make casting solution with mass fraction;
3) utilize general coating device, with step 2) casting solution that makes is coated on the membrane surface of handling through step 1, in temperature is 25～35 ℃, 30～40% times dryings of relative humidity obtain polyvinylamine-polyaniline nano fiber composite membrane, polyvinylamine-gas phase nano silica composite membrane or the polyvinylamine-ethylenediamine composite membrane of separating acid gas respectively.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102151499A (en) * | 2011-02-28 | 2011-08-17 | 浙江理工大学 | Polyamide composite nanofiltration membrane and preparation method thereof |
| CN102580563A (en) * | 2012-03-27 | 2012-07-18 | 天津大学 | Separation CO2 composite membrane prepared from micromolecule amine modification polyvinylamine and preparation |
| CN102886212A (en) * | 2012-10-10 | 2013-01-23 | 天津大学 | Method for preparing CO2 separation membrane through polyaniline nanometer material and polyvinylamine |
| CN102961978A (en) * | 2012-12-19 | 2013-03-13 | 新奥科技发展有限公司 | Polyvinylamine composite membrane and preparation method and application thereof |
| CN104801207A (en) * | 2015-01-22 | 2015-07-29 | 天津大学 | Preparation of polyvinylamine/polyaniline mixed matrix membranes used for separation of gas containing carbon dioxide |
| CN105617889A (en) * | 2014-11-05 | 2016-06-01 | 上海交通大学 | Liquid supported carbon dioxide separating membrane |
| CN109126487A (en) * | 2018-09-30 | 2019-01-04 | 太原理工大学 | A kind of electrochemical deposition method prepares polyaniline/method of polyvinylamine multilayer complex films and the application of the composite membrane |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101002999A (en) * | 2006-12-21 | 2007-07-25 | 天津大学 | Method for interfacial polymerization of fixed carrier film for separating carbon oxide |
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2009
- 2009-06-18 CN CN2009100693146A patent/CN101596412B/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102151499A (en) * | 2011-02-28 | 2011-08-17 | 浙江理工大学 | Polyamide composite nanofiltration membrane and preparation method thereof |
| CN102580563A (en) * | 2012-03-27 | 2012-07-18 | 天津大学 | Separation CO2 composite membrane prepared from micromolecule amine modification polyvinylamine and preparation |
| CN102886212A (en) * | 2012-10-10 | 2013-01-23 | 天津大学 | Method for preparing CO2 separation membrane through polyaniline nanometer material and polyvinylamine |
| CN102961978A (en) * | 2012-12-19 | 2013-03-13 | 新奥科技发展有限公司 | Polyvinylamine composite membrane and preparation method and application thereof |
| CN105617889A (en) * | 2014-11-05 | 2016-06-01 | 上海交通大学 | Liquid supported carbon dioxide separating membrane |
| CN105617889B (en) * | 2014-11-05 | 2018-05-04 | 上海交通大学 | Support liquid carbon dioxide separation film |
| CN104801207A (en) * | 2015-01-22 | 2015-07-29 | 天津大学 | Preparation of polyvinylamine/polyaniline mixed matrix membranes used for separation of gas containing carbon dioxide |
| CN109126487A (en) * | 2018-09-30 | 2019-01-04 | 太原理工大学 | A kind of electrochemical deposition method prepares polyaniline/method of polyvinylamine multilayer complex films and the application of the composite membrane |
| CN109126487B (en) * | 2018-09-30 | 2021-06-22 | 太原理工大学 | Method for preparing polyaniline/polyvinylamine multilayer composite film by electrochemical deposition method and application of composite film |
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Application publication date: 20091209 Assignee: Zhongheng new material technology (Shandong) Co.,Ltd. Assignor: Tianjin University Contract record no.: X2022980013227 Denomination of invention: Strengthened polyvinylamine fixed carrier composite membrane for separating acid gas and preparation method thereof Granted publication date: 20111109 License type: Common License Record date: 20220829 |