CN104857867A - Carbon dioxide separating membrane having both primary amine and carbonate and preparation method thereof - Google Patents
Carbon dioxide separating membrane having both primary amine and carbonate and preparation method thereof Download PDFInfo
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- CN104857867A CN104857867A CN201510232563.8A CN201510232563A CN104857867A CN 104857867 A CN104857867 A CN 104857867A CN 201510232563 A CN201510232563 A CN 201510232563A CN 104857867 A CN104857867 A CN 104857867A
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- 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]
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- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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Abstract
The invention relates to a carbon dioxide separating membrane having both primary amine and carbonate and a preparation method thereof; the method comprises the steps of preparing the polymer blends of poly (vinyl amine-diallyl dimethyl ammonium carbonate) copolymer and polyvinyl amine or poly diallyl dimethyl ammonium carbonate; taking polysulfone ultrafiltration membrane as a supporting body, dissolving the polymer blends into deionized water, and defoaming to obtain coating solution after stirring; under the condition of a certain temperature and relative humidity, carrying out drying treatment for a period of time to obtain the CO2 separating membrane having both the primary amine and the carbonate. The carbon dioxide separating membrane having both the primary amine and the carbonate realizes the synergic coupling effect between different function carriers: not only is the efficiency of the function carriers strengthened, but also the defects of various function carriers are avoided when the carriers are used alone. The carbon dioxide separating membrane having both the primary amine and the carbonate has excellent CO2 permeation selection performance: with regard to the mixed gas of CO2/N2, under the condition that the feed pressure force is 0.11-2.00 MPa, the permeation rate of the CO2 is (137-1842)*10-6, and the CO2/N2 separation factors are 23-160.
Description
Technical field
The present invention relates to poly-(vinyl amine-diallydimethyl ammonium carbonate) copolymer and polyvinylamine/diallyl dimethyl ammonium carbonate blend is the CO having primary amine groups and carbonate concurrently of material
2diffusion barrier and preparation method thereof, belongs to gas separaion technical field of membrane.
Background technology
Faciliated diffusion film is the CO that a class has application potential
2diffusion barrier.Due in film containing can with CO
2there is the function carrier of reversible action and strengthen CO
2transmission, thus Faciliated diffusion film can have high CO simultaneously
2permeability and selective, overcome the ubiquitous permeability of common polymeric membrane and selective between Trade-off effect.At present, for CO
2function carrier contained by promotes transport membranes mainly comprises amido, carboxylate radical, carbonate, fluorine ion etc.These function carriers all have respective merits and demerits.Such as: amido and CO
2reaction there is larger reaction rate constant, but 1mol primary amine groups usually can only with 0.5molCO
2reaction; And 1mol carbonate can with 1molCO
2reaction, but carbonate and CO
2reaction there is less reaction rate constant.
At present, for CO
2one of study hotspot of promotes transport membranes is for the efficiency of carrier of how strengthening function is to improve the CO of Faciliated diffusion film further
2permselective property energy.The efficiency of carrier of strengthening function mainly comprises and improves function carrier and CO
2reaction rate constant and improve the CO of function carrier
2(1mol function carrier can in conjunction with CO for chemistry reserves
2amount).He etc. select bridged piperazine derivatives to prepare CO as function carrier source
2promotes transport membranes (W.He, Z.Wang, W.Li, S.Li, Z.Bai, J.Wang, S.Wang, Cyclic tertiary amino group containing fixed carrier membranes for CO
2separation, J.Membr.Sci.476 (2015) 171-181.).Compared to alkyl tertiary amine, the tertiary amine be positioned on piperazine ring has higher reaction rate constant, and this has higher electronegativity due to the tertiary amine on piperazine ring and is easier to CO
2contact and react.Thus, be that the Faciliated diffusion film of function carrier under high pressure shows more excellent CO with cyclic tertiary amine
2selectivity.Zhao etc. have prepared the CO containing secondary sterically hindered amines
2promotes transport membranes material (Y.Zhao, W.S.W.Ho, CO
2-selective membranes containing sterically hindered amines for CO
2/ H
2separation, Ind.Eng.Chem.Res.52 (2013) 8774-8782.).Compared to without secondary sterically hindered amines, secondary sterically hindered amines has higher CO
2chemistry reserves, this is the unstability due to generated intermediate product amido carbonic ester.Thus, the Faciliated diffusion film containing secondary sterically hindered amines shows more excellent CO
2permselective property energy.Although by the efficiency that can improve function carrier through suitable structure optimization modification to a certain extent, above-mentioned CO
2function carrier all only containing single kind in promotes transport membranes, shortcoming when these function carriers are used alone still is difficult to effectively avoid, and causes function carrier efficiency to improve the limited efficiency produced.Based on this, introduced in film by different function carriers by suitable mode, the collaborative coupling realized between difference in functionality carrier is enhancement vector efficiency and then prepares high-performance for CO simultaneously
2one of potential method of promotes transport membranes.
Summary of the invention
The object of the invention is to improve CO
2in promotes transport membranes while function carrier efficiency, shortcoming when effectively avoiding various function carrier to be used alone.For this reason, this patent provides with poly-(vinyl amine-diallydimethyl ammonium carbonate) copolymer or polyvinylamine/diallyl dimethyl ammonium carbonate blend is the CO having primary amine groups and carbonate concurrently of material
2diffusion barrier and preparation method thereof.The method has been combined for CO by chemical copolymerization or physical blending means
2the difference in functionality carrier be separated, achieves the collaborative coupling effect between difference in functionality carrier: the efficiency not only enhancing function carrier, and avoids shortcoming when various function carrier is used alone.Therefore, obtained gas separation membrane shows excellent CO
2permselective property energy.
Concrete technical scheme is as follows:
Have the CO of primary amine groups and carbonate concurrently
2diffusion barrier, is characterized in that taking polysulphone super-filter membrane as basement membrane, to have the copolymer of primary amine groups and carbonate and blend concurrently for separating layer.
The preparation method of diffusion barrier of the present invention, with N-vinyl formamide and diallyldimethylammonium chloride for the method that raw material is blended after copolymerization or homopolymerization obtains the material having primary amine groups and carbonate concurrently, and then preparation coating liquid; Take polysulphone super-filter membrane as basement membrane, adopting knife coating that coating liquid is coated in membrane surface, through being dried to constant weight, obtaining the CO having primary amine groups and carbonate concurrently
2diffusion barrier.
Described copolymerization process is:
(1) be that 4:1 ~ 1:4 joins in deionized water by N-vinyl formamide and diallyldimethylammonium chloride according to mass ratio, be made into the monomer solution that mass fraction is 20%, azo-bis-isobutyrate hydrochloride is added in solution, being transferred to by solution after stirring is furnished with in the container of condenser, carries out polymerisation under nitrogen protection; After polymerisation terminates, in reaction system, add hydrochloric acid solution, be hydrolyzed reaction under nitrogen protection; The solution obtained through hydrolysis is joined in ethanol, the product of Precipitation is dissolved in deionized water and fully stirs; In solution, join strong-base anion-exchange resin, after fully stirring, carry out suction filtration process, in the solution that suction filtration obtains, add ammonium carbonate; After fully stirring, carry out dialysis treatment, the solution obtained dialysing is gathered (vinyl amine-diallydimethyl ammonium carbonate) copolymer after carrying out concentrate, dry process;
(2) poly-(vinyl amine-diallydimethyl ammonium carbonate) copolymer is dissolved in deionized water, and at room temperature ultrasonic agitation is to evenly, obtains the coating liquid that mass fraction is 1.0% ~ 4.0% after standing and defoaming.
After described homopolymerization, blend method is:
(1) acquisition polyvinylamine is polymerized by N-vinyl formamide; Be polymerized by diallyldimethylammonium chloride and obtain diallyl dimethyl ammoniumchloride; Diallyl dimethyl ammoniumchloride joined in deionized water, uniform stirring is made into the solution that mass fraction is 1.0% ~ 10.0%; In above-mentioned solution, add ammonium carbonate, its quality is 2 ~ 5 times of diallyl dimethyl ammoniumchloride; After fully stirring, solution is transferred in bag filter and carry out dialysis treatment; The solution obtained dialysing obtains diallyl dimethyl ammonium carbonate after carrying out concentrate, dry process; Be that namely 4:1 ~ 1:4 mixing obtains polyvinylamine/diallyl dimethyl ammonium carbonate blend by polyvinylamine and diallyl dimethyl ammonium carbonate according to quality;
(2) polyvinylamine/diallyl dimethyl ammonium carbonate blend is dissolved in deionized water, and at room temperature ultrasonic agitation is to evenly, obtains the coating liquid that mass fraction is 1.0% ~ 4.0% after standing and defoaming.
Have the CO of primary amine groups and carbonate concurrently
2the preparation method of diffusion barrier is:
Take molecular cut off as the polysulphone super-filter membrane of 6000 be basement membrane, adopt knife coating that coating liquid is coated in membrane surface, wet coating thickness is 50 μm ~ 300 μm, in the constant-temperature constant-humidity environment of temperature 30 DEG C and relative humidity 40%, be dried to constant weight, obtaining take poly-(vinyl amine-diallydimethyl ammonium carbonate) copolymer or polyvinylamine/diallyl dimethyl ammonium carbonate blend as the CO having primary amine groups and carbonate concurrently of material
2diffusion barrier.
The invention discloses with poly-(vinyl amine-diallydimethyl ammonium carbonate) copolymer and polyvinylamine/diallyl dimethyl ammonium carbonate blend is the CO that two kinds of material have primary amine groups and carbonate concurrently
2diffusion barrier and preparation method thereof.Poly-(vinyl amine-diallydimethyl ammonium carbonate) copolymer of preparation and polyvinylamine or diallyl dimethyl ammonium carbonate blend; Take polysulphone super-filter membrane as supporter, will gather (vinyl amine-diallydimethyl ammonium carbonate) copolymer or polyvinylamine and diallyl dimethyl ammonium carbonate blend and be dissolved in deionized water, after stirring, deaeration obtains coating liquid; Under uniform temperature and relative humidities, dry process a period of time obtains the CO having primary amine groups and carbonate concurrently
2diffusion barrier.The invention has the advantages that and prepared membrane material simultaneously containing primary amine groups and carbonate by the patten's design of chemical copolymerization and physical blending.The invention has the advantages that and prepared membrane material simultaneously containing primary amine groups and carbonate by the patten's design of chemical copolymerization and physical blending, achieve the collaborative coupling effect between difference in functionality carrier: the efficiency not only enhancing function carrier, and avoid shortcoming when various function carrier is used alone.The prices of raw and semifnished materials are cheap, and film-forming method is simple.The obtained CO having primary amine groups and carbonate concurrently
2composite membrane for separation has excellent CO
2permselective property energy: for CO
2/ N
2gaseous mixture (CO
2volume fraction is 15%), under feed gas pressure 0.11 ~ 2.00MPa condition, CO
2infiltration rate is (137 ~ 1842) × 10
-6cm
3(STP) cm
-2s
-1cmHg
-1, CO
2/ N
2separation factor is 23 ~ 160.
Accompanying drawing explanation
Fig. 1 take poly-(vinyl amine-diallydimethyl ammonium carbonate) copolymer as the CO having primary amine groups and carbonate concurrently of material obtained by embodiment 1
2the stereoscan photograph of separation membrane surface structure.
Fig. 2 take poly-(vinyl amine-diallydimethyl ammonium carbonate) copolymer as the CO having primary amine groups and carbonate concurrently of material obtained by embodiment 2
2the stereoscan photograph of diffusion barrier section structure.
Fig. 3 take poly-(vinyl amine-diallydimethyl ammonium carbonate) copolymer as the CO having primary amine groups and carbonate concurrently of material obtained by embodiment 3
2the stereoscan photograph of separation membrane surface structure.
The CO that have primary amine groups and carbonate that with polyvinylamine/diallyl dimethyl ammonium carbonate blend be material of Fig. 4 obtained by embodiment 4
2the stereoscan photograph of separation membrane surface structure.
The CO that have primary amine groups and carbonate that with polyvinylamine/diallyl dimethyl ammonium carbonate blend be material of Fig. 5 obtained by embodiment 5
2the stereoscan photograph of diffusion barrier section structure.
The CO that have primary amine groups and carbonate that with polyvinylamine/diallyl dimethyl ammonium carbonate blend be material of Fig. 6 obtained by embodiment 6
2the stereoscan photograph of separation membrane surface structure.
Detailed description of the invention
Embodiment 1
Get 8.0g N-vinyl formamide and 2.0g diallyldimethylammonium chloride joins in 40g deionized water, stir and be made into the monomer solution that mass fraction is 20%, backward solution in add azo-bis-isobutyrate hydrochloride.Being transferred to by solution after fully stirring is furnished with in the flask of condenser, carries out polymerisation under nitrogen protection.After polymerisation terminates, in reaction system, add hydrochloric acid solution, be hydrolyzed reaction under nitrogen protection.The solution obtained through hydrolysis is joined in ethanol, the product of Precipitation is dissolved in deionized water and fully stirs.In solution, join strong-base anion-exchange resin, after fully stirring, carry out suction filtration process, in the solution that suction filtration obtains, add ammonium carbonate.After fully stirring, carry out dialysis treatment, the solution obtained dialysing is gathered (vinyl amine-diallydimethyl ammonium carbonate) copolymer material after carrying out concentrate, dry process.
Getting 0.1g poly-(vinyl amine-diallydimethyl ammonium carbonate) is dissolved in 9.9g deionized water, at room temperature stirs and obtains the coating liquid that mass fraction is 1.0%.Utilization is scraped film device and is coated on polysulphone super-filter membrane by the coating liquid of above-mentioned preparation, controlling coating liquid thickness is 300 μm, then be placed in temperature 30 DEG C, the constant-temperature constant-humidity environment of humidity 40% is dried to constant weight, the CO having primary amine groups and carbonate concurrently that to obtain with polyvinylamine/diallyl dimethyl ammonium carbonate blend be material
2diffusion barrier.
The method of testing of the present embodiment and the identical of embodiment 1.Under feed gas pressure 0.11 ~ 2.00MPa condition, CO
2infiltration rate is (700 ~ 250) × 10
-6cm
3(STP) cm
-2s
-1cmHg
-1, CO
2/ N
2separation factor is 110 ~ 40.
Embodiment 2
Get 2.0gN-vinyl formamide and 8.0g diallyldimethylammonium chloride joins in 40g deionized water, stir and be made into the monomer solution that mass fraction is 20%, backward solution in add azo-bis-isobutyrate hydrochloride.Being transferred to by solution after fully stirring is furnished with in the flask of condenser, carries out polymerisation under nitrogen protection.After polymerisation terminates, in reaction system, add hydrochloric acid solution, be hydrolyzed reaction under nitrogen protection.The solution obtained through hydrolysis is joined in ethanol, the product of Precipitation is dissolved in deionized water and fully stirs.In solution, join strong-base anion-exchange resin, after fully stirring, carry out suction filtration process, in the solution that suction filtration obtains, add ammonium carbonate.After fully stirring, carry out dialysis treatment, the solution obtained dialysing is gathered (vinyl amine-diallydimethyl ammonium carbonate) copolymer material after carrying out concentrate, dry process.
Getting 0.4g poly-(vinyl amine-diallydimethyl ammonium carbonate) is dissolved in 9.6g deionized water, at room temperature stirs and obtains the coating liquid that mass fraction is 4.0%.Utilization is scraped film device and is coated on polysulphone super-filter membrane by the coating liquid of above-mentioned preparation, controlling coating liquid thickness is 50 μm, then be placed in temperature 30 DEG C, the constant-temperature constant-humidity environment of humidity 40% is dried to constant weight, the CO having primary amine groups and carbonate concurrently that to obtain with polyvinylamine/diallyl dimethyl ammonium carbonate blend be material
2diffusion barrier.
The method of testing of the present embodiment and the identical of embodiment 1.Under feed gas pressure 0.11 ~ 2.00MPa condition, CO
2infiltration rate is (500 ~ 200) × 10
-6cm
3(STP) cm
-2s
-1cmHg
-1, CO
2/ N
2separation factor is 130 ~ 60.
Embodiment 3
Get 6.0gN-vinyl formamide and 3.0g diallyldimethylammonium chloride joins in 36g deionized water, stir and be made into the monomer solution that mass fraction is 20%, backward solution in add azo-bis-isobutyrate hydrochloride.Being transferred to by solution after fully stirring is furnished with in the flask of condenser, carries out polymerisation under nitrogen protection.After polymerisation terminates, in reaction system, add hydrochloric acid solution, be hydrolyzed reaction under nitrogen protection.The solution obtained through hydrolysis is joined in ethanol, the product of Precipitation is dissolved in deionized water and fully stirs.In solution, join strong-base anion-exchange resin, after fully stirring, carry out suction filtration process, in the solution that suction filtration obtains, add ammonium carbonate.After fully stirring, carry out dialysis treatment, the solution obtained dialysing is gathered (vinyl amine-diallydimethyl ammonium carbonate) copolymer material after carrying out concentrate, dry process.
Getting 0.2g poly-(vinyl amine-diallydimethyl ammonium carbonate) is dissolved in 9.8g deionized water, at room temperature stirs and obtains the coating liquid that mass fraction is 2.0%.Utilization is scraped film device and is coated on polysulphone super-filter membrane by the coating liquid of above-mentioned preparation, controlling coating liquid thickness is 100 μm, then be placed in temperature 30 DEG C, the constant-temperature constant-humidity environment of humidity 40% is dried to constant weight, the CO having primary amine groups and carbonate concurrently that to obtain with polyvinylamine/diallyl dimethyl ammonium carbonate blend be material
2diffusion barrier.
The method of testing of the present embodiment and the identical of embodiment 1.Under feed gas pressure 0.11 ~ 2.00MPa condition, CO
2infiltration rate is (1842 ~ 300) × 10
-6cm
3(STP) cm
-2s
-1cmHg
-1, CO
2/ N
2separation factor is 160 ~ 50.
Embodiment 4
Polyvinylamine is obtained by the radical polymerization of N-vinyl formamide.Diallyl dimethyl ammoniumchloride is obtained by the radical polymerization of diallyldimethylammonium chloride.1.0g diallyl dimethyl ammoniumchloride joined in 99.0g deionized water, uniform stirring is made into the solution that mass fraction is 1.0%.In above-mentioned solution, add 5.0g ammonium carbonate, after fully stirring, solution is transferred in bag filter and carry out dialysis treatment.The solution obtained dialysing obtains diallyl dimethyl ammonium carbonate after carrying out concentrate, dry process.4.0g polyvinylamine and 1.0g diallyl dimethyl ammonium carbonate are mixed to get polyvinylamine/diallyl dimethyl ammonium carbonate blend.
Getting 0.4g polyvinylamine/diallyl dimethyl ammonium carbonate blend is dissolved in 9.6g deionized water, at room temperature stirs and obtains the coating liquid that mass fraction is 4.0%.The coating liquid of above-mentioned preparation is coated on polysulphone super-filter membrane with scraping film device, controlling coating liquid thickness is 50 μm, then be placed in temperature 30 DEG C, the constant-temperature constant-humidity environment of humidity 40% is dried to constant weight, the CO having primary amine groups and carbonate concurrently that to obtain with polyvinylamine/diallyl dimethyl ammonium carbonate blend be material
2diffusion barrier.
At ambient temperature, with CO
2/ N
2gaseous mixture (CO
2volume fraction is 15%) be unstripped gas, adopt constant voltage variable volume method to carry out gas permeability test to it.Under feed gas pressure 0.11 ~ 2.00MPa condition, CO
2infiltration rate is (350 ~ 137) × 10
-6cm
3(STP) cm
-2s
-1cmHg
-1, CO
2/ N
2separation factor is 100 ~ 35.
Embodiment 5
Polyvinylamine is obtained by the radical polymerization of N-vinyl formamide.Diallyl dimethyl ammoniumchloride is obtained by the radical polymerization of diallyldimethylammonium chloride.5.0g diallyl dimethyl ammoniumchloride joined in 45.0g deionized water, uniform stirring is made into the solution that mass fraction is 10.0%.In above-mentioned solution, add 10.0g ammonium carbonate, after fully stirring, solution is transferred in bag filter and carry out dialysis treatment.The solution obtained dialysing obtains diallyl dimethyl ammonium carbonate after carrying out concentrate, dry process.1.0g polyvinylamine and 4.0g diallyl dimethyl ammonium carbonate are mixed to get polyvinylamine/diallyl dimethyl ammonium carbonate blend.
Getting 0.1g polyvinylamine/diallyl dimethyl ammonium carbonate blend is dissolved in 9.9g deionized water, at room temperature stirs and obtains the coating liquid that mass fraction is 1.0%.Utilization is scraped film device and is coated on polysulphone super-filter membrane by the coating liquid of above-mentioned preparation, controlling coating liquid thickness is 300 μm, then be placed in temperature 30 DEG C, the constant-temperature constant-humidity environment of humidity 40% is dried to constant weight, the CO having primary amine groups and carbonate concurrently that to obtain with polyvinylamine/diallyl dimethyl ammonium carbonate blend be material
2diffusion barrier.
The method of testing of the present embodiment and the identical of embodiment 1.Under feed gas pressure 0.11 ~ 2.00MPa condition, CO
2infiltration rate is (650 ~ 200) × 10
-6cm
3(STP) cm
-2s
-1cmHg
-1, CO
2/ N
2separation factor is 85 ~ 23.
Embodiment 6
Polyvinylamine is obtained by the radical polymerization of N-vinyl formamide.Diallyl dimethyl ammoniumchloride is obtained by the radical polymerization of diallyldimethylammonium chloride.3.0g diallyl dimethyl ammoniumchloride joined in 57.0g deionized water, uniform stirring is made into the solution that mass fraction is 2.0%.In above-mentioned solution, add 12.0g ammonium carbonate, after fully stirring, solution is transferred in bag filter and carry out dialysis treatment.The solution obtained dialysing obtains diallyl dimethyl ammonium carbonate after carrying out concentrate, dry process.2.5g polyvinylamine and 2.5g diallyl dimethyl ammonium carbonate are mixed to get polyvinylamine/diallyl dimethyl ammonium carbonate blend.
Getting 0.2g polyvinylamine/diallyl dimethyl ammonium carbonate blend is dissolved in 9.8g deionized water, at room temperature stirs and obtains the coating liquid that mass fraction is 2.0%.Utilization is scraped film device and is coated on polysulphone super-filter membrane by the coating liquid of above-mentioned preparation, controlling coating liquid thickness is 50 μm, then be placed in temperature 30 DEG C, the constant-temperature constant-humidity environment of humidity 40% is dried to constant weight, the CO having primary amine groups and carbonate concurrently that to obtain with polyvinylamine/diallyl dimethyl ammonium carbonate blend be material
2diffusion barrier.
The method of testing of the present embodiment and the identical of embodiment 1.Under feed gas pressure 0.11 ~ 2.00MPa condition, CO
2infiltration rate is (1000 ~ 150) × 10
-6cm
3(STP) cm
-2s
-1cmHg
-1, CO
2/ N
2separation factor is 105 ~ 30.
Claims (4)
1. have the CO of primary amine groups and carbonate concurrently
2diffusion barrier, is characterized in that taking polysulphone super-filter membrane as basement membrane, to have the copolymer of primary amine groups and carbonate and blend concurrently for separating layer.
2. the preparation method of the diffusion barrier of claim 1, is characterized in that with N-vinyl formamide and diallyldimethylammonium chloride for the method that raw material is blended after copolymerization or homopolymerization obtains the material having primary amine groups and carbonate concurrently, and then preparation coating liquid; Take polysulphone super-filter membrane as basement membrane, adopting knife coating coating liquid to be coated in membrane surface, through being dried to constant weight, obtaining the CO having primary amine groups and carbonate concurrently
2diffusion barrier.
3. method as claimed in claim 2, is characterized in that described copolymerization process is:
(1) be that 4:1 ~ 1:4 joins in deionized water by N-vinyl formamide and diallyldimethylammonium chloride according to mass ratio, be made into the monomer solution that mass fraction is 20%, azo-bis-isobutyrate hydrochloride is added in solution, being transferred to by solution after stirring is furnished with in the container of condenser, carries out polymerisation under nitrogen protection; After polymerisation terminates, in reaction system, add hydrochloric acid solution, be hydrolyzed reaction under nitrogen protection; The solution obtained through hydrolysis is joined in ethanol, the product of Precipitation is dissolved in deionized water and fully stirs; In solution, join strong-base anion-exchange resin, after fully stirring, carry out suction filtration process, in the solution that suction filtration obtains, add ammonium carbonate; After fully stirring, carry out dialysis treatment, the solution obtained dialysing is gathered (vinyl amine-diallydimethyl ammonium carbonate) copolymer after carrying out concentrate, dry process;
(2) poly-(vinyl amine-diallydimethyl ammonium carbonate) copolymer is dissolved in deionized water, and at room temperature ultrasonic agitation is to evenly, obtains the coating liquid that mass fraction is 1.0% ~ 4.0% after standing and defoaming.
(3) take molecular cut off as the polysulphone super-filter membrane of 6000 be basement membrane, adopt knife coating that the coating liquid that (2) obtain is coated in membrane surface, wet coating thickness is 50 μm ~ 300 μm, in the constant-temperature constant-humidity environment of temperature 30 DEG C and relative humidity 40%, be dried to constant weight, obtaining with poly-(vinyl amine-diallydimethyl ammonium carbonate) copolymer is the CO that two kinds of separating layer have primary amine groups and carbonate concurrently
2diffusion barrier.
4. method as claimed in claim 2, after it is characterized in that described homopolymerization, blend method is:
(1) acquisition polyvinylamine is polymerized by N-vinyl formamide; Be polymerized by diallyldimethylammonium chloride and obtain diallyl dimethyl ammoniumchloride; Diallyl dimethyl ammoniumchloride joined in deionized water, uniform stirring is made into the solution that mass fraction is 1.0% ~ 10.0%; In above-mentioned solution, add ammonium carbonate, its quality is 2 ~ 5 times of diallyl dimethyl ammoniumchloride; After fully stirring, solution is transferred in bag filter and carry out dialysis treatment; The solution obtained dialysing obtains diallyl dimethyl ammonium carbonate after carrying out concentrate, dry process; Be that namely 4:1 ~ 1:4 mixing obtains polyvinylamine/diallyl dimethyl ammonium carbonate blend by polyvinylamine and diallyl dimethyl ammonium carbonate according to quality;
(2) polyvinylamine/diallyl dimethyl ammonium carbonate blend is dissolved in deionized water, and at room temperature ultrasonic agitation is to evenly, obtains the coating liquid that mass fraction is 1.0% ~ 4.0% after standing and defoaming.
(3) take molecular cut off as the polysulphone super-filter membrane of 6000 be basement membrane, adopt knife coating that the coating liquid that (2) obtain is coated in membrane surface, wet coating thickness is 50 μm ~ 300 μm, in the constant-temperature constant-humidity environment of temperature 30 DEG C and relative humidity 40%, be dried to constant weight, obtain with polyvinylamine/diallyl dimethyl ammonium carbonate blend two kinds of CO having primary amine groups and carbonate concurrently that are separating layer
2diffusion barrier.
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| CN109248568A (en) * | 2018-10-19 | 2019-01-22 | 天津大学 | For trapping carbon dioxide separation membrane material polyvinylamine preparation method |
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| CN103889562A (en) * | 2011-05-27 | 2014-06-25 | 康奈尔大学 | Nanoparticle-functionalized membranes, methods of making same, and uses of same |
| 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 |
| CN103071397A (en) * | 2013-01-17 | 2013-05-01 | 南京工业大学 | High-temperature CO2Method for producing separation membrane |
| CN103706263A (en) * | 2013-12-19 | 2014-04-09 | 大连理工大学 | High-flux carbon dioxide separation cellulose ethers derivative composite membrane and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109248568A (en) * | 2018-10-19 | 2019-01-22 | 天津大学 | For trapping carbon dioxide separation membrane material polyvinylamine preparation method |
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Application publication date: 20150826 Assignee: Zhongheng new material technology (Shandong) Co.,Ltd. Assignor: Tianjin University Contract record no.: X2022980013227 Denomination of invention: CO2separation membrane with both primary amine group and carbonate group and preparation method thereof Granted publication date: 20170426 License type: Common License Record date: 20220829 |