CN103041718A - Composite film with separation layer made of PVI-Zn bionic material and preparation method of composite film - Google Patents
Composite film with separation layer made of PVI-Zn bionic material and preparation method of composite film Download PDFInfo
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- CN103041718A CN103041718A CN2012105781821A CN201210578182A CN103041718A CN 103041718 A CN103041718 A CN 103041718A CN 2012105781821 A CN2012105781821 A CN 2012105781821A CN 201210578182 A CN201210578182 A CN 201210578182A CN 103041718 A CN103041718 A CN 103041718A
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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
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- 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 discloses a composite film with a separation layer made of PVI-Zn bionic material and a preparation method of the composite film. The composite film comprises a polysulphone ultrafiltration membrane as a base film, and a bionic polyvinylimidazole-zinc separation layer of 0.1-0.8 Mum thickness which is laminated on the base film. The method preparation comprises the following steps: refining and polymerizing 1-vinyl imidazole and azodiisobutyronitrile, complexing the resulting polymer with zinc acetate to make a coating liquid, pretreating a polysulphone base film, and coating the coating liquid on the base film to obtain the composite film with the PVI-Zn bionic separation layer. The preparation method of the composite film is simple and feasible, and the obtained composite film is excellent in selective permeability of CO2. With respect to a mixed gas of CO2/N2 at a volume ratio of 15 : 85, the CO2 permeation rate is (126-1147)*10<-6> cm<3>(STP)/cm<2>*s*cmHg<-1>, and the CO2/N2 separation factor is 31-83.
Description
Technical field
The present invention relates to composite membrane and preparation method that a kind of separating layer is the PVI-Zn biomimetic material, belong to the gas separation membrane technical field.
Background technology
The immobilization carrier film is a kind of novel C O
2Diffusion barrier has high CO simultaneously
2Permeability and selective is one of present study hotspot.The immobilization carrier film is mainly by carrier in the film and CO
2Reversible reaction occurs promote CO
2Diffusion.Common immobilization carrier membrane material is the polymer that contains the groups such as primary amine, secondary amine, tertiary amine, carboxylate radical, such as polyvinylamine, polypropylene amine, poly N-vinyl-GABA sodium, Sodium Polyacrylate etc.To this, the patent of delivering before the present inventor is (for separating of strengthened polyethylene imine fixed carrier composite membrane of sour gas and preparation method thereof, the patent No.: ZL200910069314; Composite membrane take carboxylate radical as immobilization carrier and preparation method thereof, the patent No.: ZL200910069313) the existing discussion.Above carrier can and CO
2Reversible action occurs, if can further improve on this basis the speed of reaction, CO
2Transfer rate in film can be higher.Carbonic anhydrase (CA) is as a kind of typical biology enzyme, can be rapidly and CO
2Reversible action occurs, catalysis CO
2Hydration, speed is up to 10
6s
-1At present, CA has been used among the liquid film, is used for CO
2Separation.But the easy inactivation of biology enzyme, unsettled feature limits its extensive use at industrial circle.Therefore, from bionical viewpoint, synthetic biomimetic material with the similar activity of CA is its key of further using.CA be a kind of macromolecule-metal complex on its structural nature, so the present invention uses the polymer-metal complex materials to serve as biomimetic material as a kind of metalloenzyme.Crystal structure studies show that the activated centre of CA is to be comprised of with the formed distortion tetrahedral structure of zinc ion coordination three histidine residues (His94, His96 and His119) and a hydrone (perhaps hydroxyl).The present invention adopts polyvinyl imidazol and the synthetic CA biomimetic material of zinc ion coordination with identical active group, and uses it for preparation CO
2Gas separates the immobilization carrier film, and the result shows that the composite membrane for preparing with this material has excellent CO
2Permeance property and CO
2/ N
2Separating property has preferably heat endurance and durability simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of separating layer is composite membrane and the preparation method of PVI-Zn biomimetic material, and this composite membrane has excellent CO
2The permselective property energy.Its preparation method is simple.
The present invention is realized by the following technical programs, a kind of separating layer is the composite membrane of polyvinyl imidazol-zinc (PVI-Zn) biomimetic material, it is characterized in that, this composite membrane with polysulphone super-filter membrane as basement membrane, composite thickness is biomimetic material polyvinyl imidazol-zinc (PVI-Zn) separating layer of 0.1 ~ 0.8 μ m on it, this composite membrane separation of C O
2Major parameter be: be the CO of 15:85 for volume ratio
2/ N
2Gaseous mixture, CO
2Infiltration rate is (126～1147) * 10
-6Cm
3(STP)/cm
2ScmHg
-1, CO
2/ N
2Separation factor is 31～83.
The separating layer of said structure is the method for the composite membrane preparation of polyvinyl imidazol-zinc (PVI-Zn) biomimetic material, it is characterized in that comprising following process:
(1) wherein polymerization inhibitor is removed in decompression distillation to raw material 1-vinyl imidazole; Initator azodiisobutyronitrile (AIBN) dissolving-recrystallization in ethanol, low temperature saves backup after the vacuum drying;
(2) the 1-vinyl imidazole monomer that will purify through step (1) and azodiisobutyronitrile (AIBN) are according to mass ratio (500-30): 1 is dissolved in toluene or the benzene, add in the reactor, then under nitrogen protection, be warming up to 65-75 ℃, reacted 2-10 hour, and generated white precipitate, obtain polyvinyl imidazol (PVI) polymer after filtering, polymer is with acetone washing three times, and is for subsequent use in 60-70 ℃ of vacuum drying afterwards;
(3) mol ratio according to zinc and polyvinyl imidazol is 1:(5-30), it is in the aqueous solution of 5%wt that the zinc acetate aqueous solution of mass fraction 1%wt is dropped to the mass fraction that the polyvinyl imidazol polymer formulation that obtained by step (2) becomes, use the HCl of 1.0M to adjust the pH value to 5-7, be stirred to abundant complexing, obtain coating liquid, standing and defoaming is for subsequent use;
(4) polysulfones (PS) milipore filter is soaked 24-48h in pretreatment fluid, the consisting of of described pretreatment fluid: mix as solvent according to mass ratio 1:50 with the second alcohol and water, mass concentration is that the lauryl sodium sulfate of 5 ‰ wt is as solute; Pretreated polysulfones (PS) milipore filter soaks half an hour with deionized water, is positioned over 30 ℃, drying for standby under the air ambient of 40% relative humidity; The thickness 30-250 μ m of control wet coating layer in the PS membrane surface, then is positioned over 30 ℃ with the composite membrane that coats with the coating liquid blade coating, and is dry under the air ambient of 40% relative humidity; Obtaining separating layer is the CO of polyvinyl imidazol-zinc (PVI-Zn) biomimetic material
2Diffusion barrier.
The invention has the advantages that the preparation method of this biomimetic material is simple, material property is stable, has the large-scale production and application prospect.With this material for the preparation of separation of C O
2The immobilization carrier film because this material has the core texture identical with carbonic anhydrase, make the immobilization carrier film have simultaneously high CO
2Permeability and selective is the CO of 15:85 for volume ratio
2/ N
2Gaseous mixture, the CO of this immobilization carrier film
2Infiltration rate is (126～1147) * 10
-6Cm
3(STP)/cm
2ScmHg
-1, CO
2/ N
2Separation factor is 31～83.
Description of drawings:
Fig. 1 is that example 1 made separating layer is the CO of polyvinyl imidazol-zinc (PVI-Zn) biomimetic material
2The surperficial electromicroscopic photograph of diffusion barrier film.
Fig. 2 is that example 1 made separating layer is the CO of polyvinyl imidazol-zinc (PVI-Zn) biomimetic material
2The section electromicroscopic photograph of diffusion barrier film.
Fig. 3 is that example 2 made separating layers are the CO of polyvinyl imidazol-zinc (PVI-Zn) biomimetic material
2The surperficial electromicroscopic photograph of diffusion barrier film.
Fig. 4 is that example 2 made separating layers are the CO of polyvinyl imidazol-zinc (PVI-Zn) biomimetic material
2The section electromicroscopic photograph of diffusion barrier film.
Fig. 5 is that example 3 made separating layers are the CO of polyvinyl imidazol-zinc (PVI-Zn) biomimetic material
2The surperficial electromicroscopic photograph of diffusion barrier film.
Fig. 6 is that example 3 made separating layers are the CO of polyvinyl imidazol-zinc (PVI-Zn) biomimetic material
2The section electromicroscopic photograph of diffusion barrier film.
The specific embodiment:
Embodiment 1 (PVI molecular weight=3.0 * 10
4
, PVI:Zn mol ratio=20:1, wet coating layer thickness=150 μ m):
The 1-vinyl imidazole that takes by weighing 100ml adds in the 250ml flask, vacuumizes to make vacuum keep at 18mmHg, is heated to 75 ℃, collects cut.Vinyl imidazole after refining is positioned in the refrigerator to be preserved.Add 5gAIBN in 50ml ethanol, place 50 ℃ water-bath heating (time is unsuitable long), slightly vibration makes it abundant dissolving.Then with the rapid suction filtration of this hot solution (filter used funnel, bottle,suction shifts to an earlier date preheating), the filtrate cooling is settled out white needle-like crystals, and 30 ℃ of lower vacuum drying, product places brown bottle after filtering, and low temperature is preserved.
10.0122g vinyl imidazole monomer, 0.2004g azodiisobutyronitrile are dissolved in the 46ml toluene.Reactant places in the there-necked flask that reflux condensing tube, electric mixer and wireway are housed, and begins to stir, and imports simultaneously nitrogen blowing.Nitrogen blowing is warming up to 70 ℃ after 10 minutes, reacted 4 hours, generates a large amount of white precipitates.Obtain product low molecular weight polyethylene base imidazoles (PVI), molecular weight 3.0 * 10 after utilizing solvent filter to filter
4Polymer washs three times with acetone, 60 ℃ of lower vacuum drying 48h.
Get 1.0052g zinc acetate (ZnAc
2), add the 100ml deionized water, be mixed with the zinc acetate solution of 1.0%wt; Get the above-mentioned polyvinyl imidazol of 0.5211g, add the 10ml deionized water, be mixed with the PVI solution of 5.0%wt; Get the PVI solution of 1.6014g5.0%wt, add 2.8001gH
2O applies magnetic agitation, slowly drips the 0.9207g zinc acetate solution simultaneously in PVI solution, makes zinc acetate and PVI solution rapid mixing even.Use the HCl solution regulator solution pH to 7 of 1.0M.After dripping end, continue to stir half an hour, obtain PVI-Zn solution, deaeration is left standstill and is obtained coating liquid.
With 0.0195m
2Polysulphone flat ultrafiltration membrane (nominal molecular cut off 6000) in pretreatment fluid, soak more than the 24h, consisting of of described pretreatment fluid: the second alcohol and water mixing 1000ml of mass ratio 1:50 is solvent, and mass concentration is that the lauryl sodium sulfate of 5 ‰ wt is solute.Polysulphone super-filter membrane is taken out from pretreatment fluid, in deionized water, soak 0.5h, dry rear for subsequent use.The coating liquid of above-mentioned preparation is coated on the treated polysulfones ultrafiltration membranes, and composite membrane wet coating layer thickness is 150 μ m.Place 30 ℃ of temperature, dry 12h in the constant-temperature constant-humidity environment of humidity 40% obtains take polysulfones as basement membrane the separation of C O take biomimetic material polyvinyl imidazol-zinc as separating layer again
2Composite membrane, composite membrane separating layer thickness are 0.704 μ m.Be the CO of 15:85 with volume ratio
2/ N
2Gaseous mixture carries out performance test to composite membrane, when feed gas pressure is 0.11～1.6MPa, and CO
2Infiltration rate is (391～168) * 10
-6Cm
3(STP)/cm
2ScmHg
-1, CO
2/ N
2Separation factor be 67～34.
Embodiment 2 (PVI molecular weight=3.0 * 10
4
, PVI:Zn mol ratio=10:1, wet coating layer thickness=150 μ m):
Carry out the feed purification preliminary treatment according to the method in the example 1.10.0122g vinyl imidazole monomer, 0.2004g azodiisobutyronitrile are dissolved in the 46ml toluene.Reactant places in the there-necked flask that reflux condensing tube, electric mixer and wireway are housed, and begins to stir, and imports simultaneously nitrogen blowing.Nitrogen blowing is warming up to 70 ℃ after 10 minutes, reacted 4 hours, generates a large amount of white precipitates.Obtain product low molecular weight polyethylene base imidazoles (PVI), molecular weight 3.0 * 10 after utilizing solvent filter to filter
4Polymer washs three times with acetone, 60 ℃ of lower vacuum drying 48h.
Get 1.0052g zinc acetate (ZnAc
2), add the 100ml deionized water, be mixed with the zinc acetate solution of 1.0%wt; Get the above-mentioned polyvinyl imidazol of 0.5211g, add the 10ml deionized water, be mixed with the PVI solution of 5.0%wt; Get the PVI solution of 1.6002g5.0%wt, add 1.9018gH
2O applies magnetic agitation, slowly drips the 1.8507g zinc acetate solution simultaneously in PVI solution, makes zinc acetate and PVI solution rapid mixing even.Use the HCl solution regulator solution pH to 7 of 1.0M.After dripping end, continue to stir half an hour, the deaeration of acquisition PVI-Zn solution is left standstill and is obtained coating liquid.
With 0.0195m
2Polysulphone flat ultrafiltration membrane (nominal molecular cut off 6000) according to the method preliminary treatment in the example 1.The coating liquid of above-mentioned preparation is coated on the treated polysulfones ultrafiltration membranes, and composite membrane wet coating layer thickness is 150 μ m.Place 30 ℃ of temperature, dry 12h in the constant-temperature constant-humidity environment of humidity 40% obtains take polysulfones as basement membrane the separation of C O take biomimetic material polyvinyl imidazol-zinc as separating layer again
2Composite membrane, composite membrane separating layer thickness are 0.703 μ m.Be the CO of 15:85 with volume ratio
2/ N
2Gaseous mixture carries out performance test to composite membrane, when feed gas pressure is 0.11～1.6MPa, and CO
2Infiltration rate is (439～234) * 10
-6Cm
3(STP)/cm
2ScmHg
-1, CO
2/ N
2Separation factor be 75～40.
Embodiment 3(PVI molecular weight=1.7 * 10
6
, PVI:Zn mol ratio=10:1, wet coating layer thickness=50 μ m):
Carry out the feed purification preliminary treatment according to the method in the example 1.10.0063g vinyl imidazole monomer, 0.0344g azodiisobutyronitrile are dissolved in the 30ml benzene.Reactant places in the there-necked flask that reflux condensing tube, electric mixer and wireway are housed, and begins to stir, and imports simultaneously nitrogen blowing.Nitrogen blowing is warming up to 70 ℃ after 10 minutes, reacted 7 hours, generates a large amount of white precipitates.Obtain product High molecular weight polyethylene base imidazoles (PVI), molecular weight 1.7 * 10 after utilizing solvent filter to filter
6With acetone washing three times, 60 ℃ of lower vacuum drying 48h.
Get 1.0052g zinc acetate (ZnAc
2), add the 100ml deionized water, be mixed with the zinc acetate solution of 1.0%wt; Get the above-mentioned polyvinyl imidazol of 0.5209g, add the 10ml deionized water, be mixed with the PVI solution of 5.0%wt; Get the PVI solution of 1.6017g5.0%wt, add 1.9045gH
2O applies magnetic agitation, slowly drips the 1.8511g zinc acetate solution simultaneously in PVI solution, makes zinc acetate and PVI solution rapid mixing even.Use the HCl solution regulator solution pH to 5 of 1.0M.After dripping end, continue to stir half an hour, the deaeration of acquisition PVI-Zn solution is left standstill and is obtained coating liquid.
With 0.0195m
2Polysulphone flat ultrafiltration membrane (nominal molecular cut off 6000) according to the method preliminary treatment in the example 1.The coating liquid of above-mentioned preparation is coated on the treated polysulfones ultrafiltration membranes, and composite membrane wet coating layer thickness is 50 μ m.Place 30 ℃ of temperature, dry 12h in the constant-temperature constant-humidity environment of humidity 40% obtains take polysulfones as basement membrane the separation of C O take biomimetic material polyvinyl imidazol-zinc as separating layer again
2Composite membrane, composite membrane separating layer thickness are 0.122 μ m.Be the CO of 15:85 with volume ratio
2/ N
2Gaseous mixture carries out performance test to composite membrane, when feed gas pressure is 0.11～1.6MPa, and CO
2Infiltration rate is (1147～288) * 10
-6Cm
3(STP)/cm
2ScmHg
-1, CO
2/ N
2Separation factor be 83～36.
Claims (2)
1. the composite membrane that separating layer is polyvinyl imidazol-zinc biomimetic material is characterized in that, as basement membrane, composite thickness is the biomimetic material polyvinyl imidazol-zinc separating layer of 0.1 ~ 0.8 μ m to this composite membrane on it, this composite membrane separation of C O with polysulphone super-filter membrane
2Major parameter be: be the CO of 15:85 for volume ratio
2/ N
2Gaseous mixture, CO
2Infiltration rate is (126～1147) * 10
-6Cm
3(STP)/cm
2ScmHg
-1, CO
2/ N
2Separation factor is 31～83.
2. one kind is the method for the composite membrane preparation of polyvinyl imidazol-zinc biomimetic material by separating layer claimed in claim 1, it is characterized in that comprising following process:
Polymerization inhibitor is wherein removed in decompression distillation to raw material 1-vinyl imidazole; Initator azodiisobutyronitrile dissolving-recrystallization in ethanol, low temperature saves backup after the vacuum drying;
Will be through 1-vinyl imidazole monomer that step 1) is purified and azodiisobutyronitrile according to mass ratio (500-30): 1 be dissolved in toluene or the benzene, add in the reactor, then under nitrogen protection, be warming up to 65-75 ℃, reacted 2-10 hour, and generated white precipitate, obtain the polyvinyl imidazol polymer after filtering, polymer is with acetone washing three times, and is for subsequent use in 60-70 ℃ of vacuum drying afterwards;
Mol ratio according to zinc and polyvinyl imidazol is 1:(5-30), the zinc acetate aqueous solution of mass fraction 1%wt is dropped to by step 2) mass fraction that becomes of the polyvinyl imidazol polymer formulation that obtains is in the aqueous solution of 5%wt, use the HCl of 1.0M to adjust the pH value to 5-7, be stirred to abundant complexing, obtain coating liquid, standing and defoaming is for subsequent use;
Polysulphone super-filter membrane is soaked 24-48h in pretreatment fluid, the consisting of of described pretreatment fluid: mix as solvent according to mass ratio 1:50 with the second alcohol and water, mass concentration is that the lauryl sodium sulfate of 5 ‰ wt is as solute; Pretreated polysulphone super-filter membrane soaks half an hour with deionized water, is positioned over 30 ℃, drying for standby under the air ambient of 40% relative humidity; The thickness 30-250 μ m of control wet coating layer in the polysulfones membrane surface, then is positioned over 30 ℃ with the composite membrane that coats with the coating liquid blade coating, and is dry under the air ambient of 40% relative humidity; Obtaining separating layer is the composite membrane of polyvinyl imidazol-zinc biomimetic material.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104103874A (en) * | 2014-05-24 | 2014-10-15 | 渤海大学 | Preparation method and application of polyion liquid based solid electrolyte |
| WO2016162518A1 (en) * | 2015-04-08 | 2016-10-13 | Norwegian University Of Science And Technology (Ntnu) | Composite membrane |
| CN111841338A (en) * | 2019-04-25 | 2020-10-30 | 北京化工大学 | Fixed carrier composite membrane for separating carbon dioxide and preparation method thereof |
| CN112423867A (en) * | 2018-04-30 | 2021-02-26 | 辛特福特图有限公司 | Carbon dioxide separation membrane comprising carbonic anhydrase |
| CN115386038A (en) * | 2022-09-02 | 2022-11-25 | 北京化工大学 | Preparation method and application of carbonic anhydrase mimic enzyme |
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| CN101844042A (en) * | 2010-05-21 | 2010-09-29 | 厦门大学 | Preparation method of anion-exchange membranes based on ionic liquid |
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| CN101844042A (en) * | 2010-05-21 | 2010-09-29 | 厦门大学 | Preparation method of anion-exchange membranes based on ionic liquid |
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|---|
| KAI YAO，ET AL: "Biomimetic material—poly(N-vinylimidazole)–zinc complex for CO2", 《CHEMCOMM》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104103874A (en) * | 2014-05-24 | 2014-10-15 | 渤海大学 | Preparation method and application of polyion liquid based solid electrolyte |
| CN104103874B (en) * | 2014-05-24 | 2016-04-06 | 渤海大学 | A kind of preparation method of poly ion liquid base solid electrolyte and application thereof |
| WO2016162518A1 (en) * | 2015-04-08 | 2016-10-13 | Norwegian University Of Science And Technology (Ntnu) | Composite membrane |
| CN112423867A (en) * | 2018-04-30 | 2021-02-26 | 辛特福特图有限公司 | Carbon dioxide separation membrane comprising carbonic anhydrase |
| CN111841338A (en) * | 2019-04-25 | 2020-10-30 | 北京化工大学 | Fixed carrier composite membrane for separating carbon dioxide and preparation method thereof |
| CN111841338B (en) * | 2019-04-25 | 2021-10-15 | 北京化工大学 | Fixed carrier composite membrane for separating carbon dioxide and preparation method thereof |
| CN115386038A (en) * | 2022-09-02 | 2022-11-25 | 北京化工大学 | Preparation method and application of carbonic anhydrase mimic enzyme |
| CN115386038B (en) * | 2022-09-02 | 2024-03-26 | 北京化工大学 | Preparation method and application of carbonic anhydrase mimic enzyme |
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Application publication date: 20130417 |