CN105727767A - Preparation and application of asymmetric facilitated transport membrane - Google Patents

Preparation and application of asymmetric facilitated transport membrane Download PDF

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Publication number
CN105727767A
CN105727767A CN201610235155.2A CN201610235155A CN105727767A CN 105727767 A CN105727767 A CN 105727767A CN 201610235155 A CN201610235155 A CN 201610235155A CN 105727767 A CN105727767 A CN 105727767A
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asymmetric
film
preparation
membrane
polyether sulfone
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Inventor
姜忠义
王少飞
霍亭丞
彭冬冬
吴英震
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Tianjin University
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Tianjin University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/22—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/022—Asymmetric membranes

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention discloses a preparation method of an asymmetric facilitated transport membrane.The preparation method includes the steps that polyether sulfone is dissolved in a mixed solution of N,N-dimethylformamide and tetrahydrofuran; polyethyleneimine is added and stirred to be dissolved, an obtained nascent-state membrane is scraped onto a glass plate, and the glass plate is put into a gel bath for membrane forming; the asymmetric facilitated transport membrane is obtained after exchange of a membrane solvent.The preparation method is simple and can be used for preparing the asymmetric membrane with the surface containing facilitated transport functional groups in a one-step process, and the prepared composite membrane is used for gas separation and has excellent overall performance.The molecular weight of polyethyleneimine is 10000, the addition amount of polyethyleneimine is 20% the mass fraction of polyether sulfone, and the asymmetric facilitated transport membrane prepared with the gel bath with the mixture volume ratio of ethyl alcohol/isopropyl alcohol being 1/1 has high CO2 permeation flux and high CO2/CH4 selectivity and CO2/N2 selectivity; in a mixed gas test under the humidification condition, the CO2 permeation flux can reach 175 GPU, the CO2/CH4 selectivity is 42, and the CO2/N2 selectivity is 38.

Description

The preparation of a kind of asymmetric faciliated diffusion film and application
Technical field
The present invention relates to preparation and the application of a kind of asymmetric faciliated diffusion film, belong to gas membrane Seperation Technology field.
Background technology
In the last few years, greenhouse effect had become as the severe environmental problem of a globalization.Wherein CO2As topmost Greenhouse gases, its discharge capacity grows with each passing day along with industrial expansion and the burning of a large amount of Fossil fuel, so to CO2Row The most effectively control just to seem particularly urgent and important, and control CO2The key of discharge capacity is exactly CO2Trapping with Isolation technics.At numerous CO2In isolation technics, membrane separating CO2With it efficiently, the advantage such as energy-saving and environmental protection obtained generation The most attention of various countries of boundary, becomes the emerging industry having a high potential.
Preferably CO2Separate film and should have the feature that permeability and the selectivity of excellence；Relatively low cost；Good Processing characteristics and mechanical performance；Good physical and chemical stability.It is good that high-molecular organic material has low cost, processing characteristics In actual industrial, advantage is had more etc. feature.There is the anisotropic membrane of porous support layer and dense separation layers because having flux The features such as height, good stability, are the membrane structure forms of the most most industrial prospect.At present about faciliated diffusion anisotropic membrane Preparation method rarely have report, it would be highly desirable to need to develop efficient membrane material, faciliated diffusion mechanism be integrated in anisotropic membrane.
Summary of the invention
It is an object of the invention to the preparation method and application of a kind of asymmetric faciliated diffusion film.That prepares in this approach is asymmetric Faciliated diffusion film is used for separating CO2/CH4、CO2/N2Mixture, has higher CO2Infiltration rate and separation factor.
The present invention is achieved through the following technical solutions, a kind of asymmetric faciliated diffusion film, and key component is polyether sulfone, with Polymine is as modifying agent, and this film is prepared by non-solvent induction phase inversion；Wherein, the addition of polymine For polyether sulfone 5-40% mass fraction；The molecular weight of polymine is 600-70000.
The preparation method of above-mentioned asymmetric faciliated diffusion film, comprises the following steps:
Step one, the polyether sulfone of certain mass is dissolved in N,N-dimethylformamide obtains in the mixed solution of oxolane Solution A, wherein, polyether sulfone content accounts for the matter of the 30% of solution A gross mass, DMF and oxolane Amount ratio is 3:1；
Step 2, it is 5-40% according to the mass fraction of polymine Yu polyether sulfone, is the poly-of 600-70000 by molecular weight Aziridine joins in the solution A that step one obtains as modifying agent, is placed in mechanical agitation 4-6 in 60 DEG C of waters bath with thermostatic control H obtains casting solution；
Step 3, after casting solution is cooled to room temperature with strainer filtering, be poured on clean glass plate, with scraper at glass The nascent state film of 200-240 μ m-thick is scraped on plate；
Step 4, until solvent volatilization 10s-1min after, by attachment nascent state film glass plate immerse rapidly the gel under room temperature In bath；Film after gel precipitation is taken off and is placed in clear water immersion 24-48h, to remove solvent and free modifying agent；Hygrometric state Nascent state film take out from deionized water after, first use ethanol carry out 3 solvent exchange, each 2h；Enter with normal heptane again 3 solvent exchange of row, each 2h；Then the film through solvent exchange is placed in climatic chamber, at 30 DEG C, 40%R.H. Under dry after be asymmetric faciliated diffusion film.
Further, in the step 4 of above-mentioned preparation method, coagulation bath is the mixture of ethanol and isopropanol, wherein, ethanol with The volume ratio of isopropanol is 1:1-1:8.
The asymmetric faciliated diffusion film of the present invention is used for gas separate, especially for CO2/CH4Or CO2/N2Separation.
It is an advantage of the current invention that: preparation method is simple, one-step method can prepare surface and contain the asymmetric of faciliated diffusion functional group Film, obtained composite membrane separates for gas, has the combination property of excellence.Especially, using molecular weight is 10000 Polymine, the addition of polymine is that the asymmetric compound film of the concentration of PES 20% has high CO2 Permeation flux and CO2/CH4、CO2/N2Selectivity, gaseous mixture test CO under humidified condition2Permeation flux up to 175GPU, CO2/CH4Selectivity is 42, CO2/N2Selectivity is 38.
Detailed description of the invention
Being described in further detail technical solution of the present invention below in conjunction with specific embodiment, described specific embodiment is the most right The present invention explains, not in order to limit the present invention.
Embodiment 1, the preparation of a kind of asymmetric faciliated diffusion film, step is as follows:
Step one, 10g polyether sulfone is dissolved in the mixed solution of 23.3g DMF and oxolane, its In, DMF is 3/1 with the mass ratio of oxolane.
Step 2, the mixed solution that the polymine that 2g molecular weight is 10000 is obtained as modifying agent addition above-mentioned steps In, it is placed in the casting solution that mechanical agitation 4h in 60 DEG C of waters bath with thermostatic control obtains dissolving.
Step 3, after casting solution is cooled to room temperature with strainer filtering, be poured on clean glass plate, with scraper at glass The nascent state film of about 240 μ m-thick is scraped on plate.
Step 4, after solvent volatilization 10s, the glass plate of attachment nascent state film is immersed rapidly in the coagulation bath under room temperature, solidifying Ethanol/isopropanol the volume ratio that consists of of glue bath is 1/1.Film after gel precipitation is taken off and is placed in clear water immersion 24h, to remove Remove solvent and free modifying agent.After the support membrane of hygrometric state takes out from deionized water, first use ethanol to carry out 3 solvents and hand over Change, be 2h every time；3 solvent exchange, each 2h is carried out again with normal heptane；Then take out and be placed in climatic chamber, 30 DEG C, dry under 40%R.H. after be asymmetric faciliated diffusion film.
By prepared asymmetric faciliated diffusion film under the dry state test condition that room temperature, test pressure are 1bar, separate CO2Body Fraction is the N of 20%2-CO2Binary gas, CO2Infiltration rate is 175GPU (1GPU=10-6cm3(STP)/(cm2 S cmHg)), CO2/N2Separation factor is 38, under the same conditions, separates CO2Volume fraction is the CH of 30%4-CO2 Binary gas, CO2/CH4Separation factor is 42.
Embodiment 2, the preparation of a kind of asymmetric faciliated diffusion film, preparation method is basically identical with embodiment 1, and difference exists In: in step 4, in coagulation bath, ethanol/isopropanol volume ratio is 1/8.
Test condition is same as in Example 1, separates CO2Volume fraction is the N of 20%2-CO2Binary gas, CO2Infiltration Speed is 138GPU, CO2/N2Separation factor is 22, under the same conditions, separates CO2Volume fraction is the CH of 30%4-CO2 Binary gas, CO2/CH4Separation factor is 32.
Embodiment 3, the preparation of a kind of asymmetric faciliated diffusion film, preparation method is basically identical with embodiment 1, and difference exists In: in step 2, the addition of polymine is 0.5g.
Test condition is same as in Example 1, separates CO2Volume fraction is the N of 20%2-CO2Binary gas, CO2Infiltration Speed is 77GPU, CO2/N2Separation factor is 32, under the same conditions, separates CO2Volume fraction is the CH of 30%4-CO2 Binary gas, CO2/CH4Separation factor is 38.
Embodiment 4, the preparation of a kind of asymmetric faciliated diffusion film, preparation method is basically identical with embodiment 1, and difference exists In: in step 2, the addition of polymine is 4g.
Test condition is same as in Example 1, separates CO2Volume fraction is the N of 20%2-CO2Binary gas, CO2Infiltration Speed is 289GPU, CO2/N2Separation factor is 14, under the same conditions, separates CO2Volume fraction is the CH of 30%4-CO2 Binary gas, CO2/CH4Separation factor is 17.
Embodiment 5, the preparation of a kind of asymmetric faciliated diffusion film, preparation method is basically identical with embodiment 1, and difference exists In: in step 2, the molecular weight of the polymine of addition is 600.
Test condition is same as in Example 1, separates CO2Volume fraction is the N of 20%2-CO2Binary gas, CO2Infiltration Speed is 55GPU, CO2/N2Separation factor is 26, under the same conditions, separates CO2Volume fraction is the CH of 30%4-CO2 Binary gas, CO2/CH4Separation factor is 33.
Embodiment 6, the preparation of a kind of asymmetric faciliated diffusion film, preparation method is basically identical with embodiment 1, and difference exists In: in step 2, the molecular weight of the polymine of addition is 70000.
Test condition is same as in Example 1, separates CO2Volume fraction is the N of 20%2-CO2Binary gas, CO2Infiltration Speed is 652GPU, CO2/N2Separation factor is 11, under the same conditions, separates CO2Volume fraction is the CH of 30%4-CO2 Binary gas, CO2/CH4Separation factor is 8.
Comparative example 1, the preparation of a kind of asymmetric promotion film, step is as follows:
Step one, 10g polyether sulfone is dissolved in 30g N,N-dimethylformamide and the mixed solution of oxolane prepare molten Liquid A, wherein, DMF is 3/1 with the mass ratio of oxolane, and above-mentioned solution A is placed in 60 DEG C of perseverances In tepidarium, mechanical agitation 4h obtains the casting solution dissolved.
Step 2, after casting solution is cooled to room temperature with strainer filtering, be poured on clean glass plate, with scraper at glass The nascent state film of about 240 μ m-thick is scraped on plate.
Step 3, after solvent volatilization 10s, the glass plate of attachment nascent state film is immersed rapidly in the coagulation bath under room temperature, solidifying Ethanol/isopropanol the volume ratio that consists of of glue bath is 1/1.Film after gel precipitation is taken off and is placed in clear water immersion 24h, to remove Remove solvent.After the support membrane of hygrometric state takes out from deionized water, first use ethanol to carry out 3 solvent exchange, be 2h every time； 3 solvent exchange, each 2h is carried out again with normal heptane；Then take out and be placed in climatic chamber, at 30 DEG C, 40%R.H. Under dry after be anisotropic membrane.
By above-mentioned prepared anisotropic membrane under the dry state test condition that room temperature, test pressure are 1bar, separate CO2Volume integral Number is the N of 20%2-CO2Binary gas, CO2Infiltration rate is 175GPU (1GPU=10-6cm3(STP)/(cm2s CmHg)), CO2/N2Separation factor is 38, under the same conditions, separates CO2Volume fraction is the CH of 30%4-CO2Two Unit's gaseous mixture, CO2/CH4Separation factor is 42.
To sum up, along with the increase of the volume ratio of ethanol/isopropanol, CO2Infiltration rate and CO2/N2, CO2/CH4Selection Property increase.Along with the addition of polymine increases, CO2Infiltration rate and CO2/N2, CO2/CH4Selectivity first Reduce after increase, when the addition of polymine is the concentration of PES 20%, maximum occurs.Along with polyethyleneimine The increase of amine molecule amount, CO2Infiltration rate and CO2/N2, CO2/CH4Selectivity first increases and then decreases, at polyethylene Imines molecular weight is maximum occur when 10000.
Although above, invention has been described, but the invention is not limited in above-mentioned detailed description of the invention, above-mentioned Detailed description of the invention is only schematic rather than restrictive, and those of ordinary skill in the art is in the enlightenment of the present invention Under, without deviating from the spirit of the invention, it is also possible to make many variations, within these belong to the protection of the present invention.

Claims (4)

1. an asymmetric faciliated diffusion film, it is characterised in that key component is polyether sulfone, using polymine as modification Agent, this film is prepared by non-solvent induction phase inversion；Wherein, the addition of polymine is polyether sulfone 5-40% mass Mark；The molecular weight of polymine is 600-70000.
2. the preparation method of an asymmetric faciliated diffusion film as claimed in claim 1, it is characterised in that comprise the following steps:
Step one, the polyether sulfone of certain mass is dissolved in N,N-dimethylformamide obtains in the mixed solution of oxolane Solution A, wherein, polyether sulfone content accounts for the matter of the 30% of solution A gross mass, DMF and oxolane Amount ratio is 3:1；
Step 2, it is 5-40% according to the mass fraction of polymine Yu polyether sulfone, is the poly-of 600-70000 by molecular weight Aziridine joins in the solution A that step one obtains as modifying agent, is placed in mechanical agitation 4-6 in 60 DEG C of waters bath with thermostatic control H obtains casting solution；
Step 3, after casting solution is cooled to room temperature with strainer filtering, be poured on clean glass plate, with scraper at glass The nascent state film of 200-240 μ m-thick is scraped on plate；
Step 4, until solvent volatilization 10s-1min after, by attachment nascent state film glass plate immerse rapidly the gel under room temperature In bath；Film after gel precipitation is taken off and is placed in clear water immersion 24-48h, to remove solvent and free modifying agent；Hygrometric state Nascent state film take out from deionized water after, first use ethanol carry out 3 solvent exchange, each 2h；Enter with normal heptane again 3 solvent exchange of row, each 2h；Then the film through solvent exchange is placed in climatic chamber, at 30 DEG C, 40%R.H. Under dry after be asymmetric faciliated diffusion film.
Asymmetric faciliated diffusion film the most as claimed in claim 2 preparation method, it is characterised in that coagulation bath in step 4 Being the mixture of ethanol and isopropanol, wherein, ethanol is 1:1-1:8 with the volume ratio of isopropanol.
4. the application of the asymmetric faciliated diffusion film that preparation method as described in Claims 2 or 3 prepares, it is characterised in that use In CO2/CH4Or CO2/N2Gas separate in.
CN201610235155.2A 2016-04-13 2016-04-13 Preparation and application of asymmetric facilitated transport membrane Pending CN105727767A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1710011A1 (en) * 2005-04-07 2006-10-11 Gambro Lundia AB Filtration membrane
CN101002999A (en) * 2006-12-21 2007-07-25 天津大学 Method for interfacial polymerization of fixed carrier film for separating carbon oxide
CN104056557A (en) * 2014-06-18 2014-09-24 南京理工大学 Polyether sulfone ultrafiltration membrane preparation method capable of improving permeability and selectivity simultaneously
CN104524990A (en) * 2014-12-15 2015-04-22 南京工业大学 Gas separation membrane, preparation method thereof and membrane type gas separation device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1710011A1 (en) * 2005-04-07 2006-10-11 Gambro Lundia AB Filtration membrane
CN101002999A (en) * 2006-12-21 2007-07-25 天津大学 Method for interfacial polymerization of fixed carrier film for separating carbon oxide
CN104056557A (en) * 2014-06-18 2014-09-24 南京理工大学 Polyether sulfone ultrafiltration membrane preparation method capable of improving permeability and selectivity simultaneously
CN104524990A (en) * 2014-12-15 2015-04-22 南京工业大学 Gas separation membrane, preparation method thereof and membrane type gas separation device

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