CN106390780A - Modified polyimide hollow fiber gas separation membrane, modification method and applications thereof - Google Patents
Modified polyimide hollow fiber gas separation membrane, modification method and applications thereof Download PDFInfo
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- CN106390780A CN106390780A CN201510455064.5A CN201510455064A CN106390780A CN 106390780 A CN106390780 A CN 106390780A CN 201510455064 A CN201510455064 A CN 201510455064A CN 106390780 A CN106390780 A CN 106390780A
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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]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The invention provides a modified polyimide hollow fiber gas separation membrane, a modification method and applications thereof. The method comprises: carrying out irradiation modification treatment on a polyimide hollow fiber gas separation membrane by using ionizing radiation to obtain the modified polyimide hollow fiber gas separation membrane. The invention further provides the modified polyimide hollow fiber gas separation membrane obtained through the modification method, and applications of the modified polyimide hollow fiber gas separation membrane in biogas CO2 removal. According to the present invention, the modified polyimide hollow fiber gas separation membrane has excellent heat resistance, excellent organic solvent resistance, and excellent mechanical properties; and with the application of the modified polyimide hollow fiber gas separation membrane in biogas CO2 removal, the good separation effect is provided for CO2/CH4 mixed gas, the high selectivity and the high permeability are provided, and the CO2 gas permeability coefficient can be substantially improved.
Description
Technical field
The present invention relates to a kind of modified polyimide Ho llow fiber membrane for gas separation and method of modifying and application, belong to high score
Sub- field of material technology.
Background technology
As a super-huge energy-consuming city, Renewable Energy Development is to realizing energy-saving and emission-reduction, alleviate the energy in Beijing
Crisis, Optimization of Energy Structure, developing a circular economy etc. has important effect.Can have especially with biomass energy
Effect solves the pollution problems such as municipal refuse, feces of livestock and poultry, agricultural crop straw.Compared with solar energy, wind energy, with biology
Methane is the biomass energy of Typical Representative is the renewable energy that uniquely can store, can use as fuel and chemical raw material
Source.Methane producing biological methane mainly needs, through purifying and purifying, to purify and remove micro harmful constituent in biogas, carry
Pure primarily to remove biogas in CO2, remove CO2It is main task.The biological first obtaining through purification
Alkane, usually contains the methane of 95%-97%, alternative natural gas motorcar.CO in biogas2Removing sulfuldioxide mainly have
The methods such as high-pressure washing, pressure-variable adsorption, physical absorption, chemical absorbing and membrance separation.Wherein membrane separation process has and separates
The advantages of efficiency high, floor space are little, energy consumption is relatively low, easy and simple to handle, maintenance is easy, before showing preferable application
Scape.
Seperation film has various ways, such as Flat Membrane, tubular membrane, hollow-fibre membrane, and wherein hollow-fibre membrane is profile
As threadiness, there is the hollow membrane of self-supporting effect.Hollow-fibre membrane has that loading density is high, specific surface area is big, resistance to
Pressure performance is good, the advantages of membrane module structure is simple, corresponding Middle hollow fiber membrane process has that energy consumption is low, apparatus body
Long-pending little and easy to operate, high efficiency, the features such as do not produce secondary pollution, increasingly it is widely applied.
Contain imide ring on polyimides main chain, there is excellent thermostability, organic solvent resistance and superior mechanical
Performance, is a kind of more gas separation material of research.Due to having sufficiently stable heteroaromatic structure in molecule, gather
This glassy polymers of acid imide have higher gas-selectively, especially have the aromatic series of stiff backbone construction
PI is more preferable for the detached selectivity of gas.Therefore, excellent gas is had by seperation film prepared by polyimide material
Body separating property.PI film can be used for the separation of multiple gases, as carbon dioxide/methane or nitrogen, nitrogen/oxygen, hydrogen/nitrogen etc.
Separate, the moisture in removing alcohols and air hydrocarbon raw material gas, it may also be used for ultrafilter membrane and osmotic evaporation film.
Gamma-radiation radiotechnology obtains more and more wider as a kind of green production processing mode of civilian non-powered nuclear technology
General application.Radiotechnology is macromolecular material preparation, a kind of modified effective means, and its advantage is：(1) it is being subject to
Irradiate in thing and generate free radical or ion, thus causing radiation polymerization, radiation grafting, crosslinking with radiation or radiation degradation anti-
Should, with relatively simple technology synthesis or modified polymer material；(2) without initiator or additive, products pure；
(3) radiation synthesis or modification can be carried out under room temperature or low temperature (polymer glass state temperature), to thermal sensitivity biomaterial ten
Divide favourable.Compared with traditional chemical industry, radiation chemistry industrial product quality is good, public hazards are few, process is simple, cost
Cheap, energy expenditure is low.
Content of the invention
It is an object of the invention to provide a kind of method of modifying of polyimide hollow fiber gas separation membrane.
The present invention also aims to providing a kind of method of modifying by above-mentioned polyimide hollow fiber gas separation membrane
The modified polyimide Ho llow fiber membrane for gas separation obtaining.
The present invention also aims to providing above-mentioned modified polyimide Ho llow fiber membrane for gas separation in removing biogas
CO2Application.
For reaching above-mentioned purpose, the invention provides a kind of method of modifying of polyimide hollow fiber gas separation membrane, should
Method comprises the following steps：Using ionizing radiation, polyimide hollow fiber gas separation membrane is carried out at radiation modification
Reason, obtains the polyimide hollow fiber gas separation membrane of described modified process.
According to the preferred embodiment of the present invention, described radiation absorber amount is 15-200kGy.
According to the preferred embodiment of the present invention, described ionizing radiation includes gamma-rays and X-ray；Described gamma-rays enter
One step includes60Co- gamma-rays and137Cs- gamma-rays.
According to the preferred embodiment of the present invention, described irradiation is at room temperature, under air, limit oxygen or oxygen free condition
Carry out.
According to the preferred embodiment of the present invention, above-mentioned limit oxygen process is this area conventional technique means, this area skill
Art personnel can need to select suitable limit oxygen method, in a preferred embodiment of the invention, limit according to field operation
Oxygen is first sample to be placed in sealing in hermetic bag, then carries out gamma-ray irradiation again.
According to the preferred embodiment of the present invention, the preparation of described polyimides comprises the following steps：Using aromatic diamines
Prepare polyimides with aromatic dianhydride.
According to the preferred embodiment of the present invention, the mol ratio of described aromatic dianhydride and aromatic diamines is 0.9-1.5:1.
According to the preferred embodiment of the present invention, the preparation of described polyimides follows the steps below：
(1), under inert atmosphere, aromatic diamines and aromatic dianhydride are dissolved in aprotic polar solvent, obtain solution
A, solution A is reacted 4-24h under -30 DEG C to room temperature, obtains polyamic acid solution；
The mass concentration (being counted with solute aromatic dianhydride and aromatic diamines) of described solution A is as 20-30wt%；
(2), the polyamic acid solution obtaining to step (1) adds acetic anhydride and pyridine, stirs under room temperature, reaction
12-24h；Products therefrom will be reacted add in ethanol, stir to guarantee to reel off raw silk from cocoons, more after drying, obtain polyamides sub-
Amine.
In the preferred embodiment of the present invention, above-mentioned steps (1) can follow the steps below：By fragrance two
Amine monomers are dissolved in aprotic polar solvent, stir, and temperature of reaction system is down to 0 DEG C by ice bath, adds
Aromatic dianhydride monomer, 0 DEG C of reaction 4-24h, obtain polyamic acid solution.
According to the preferred embodiment of the present invention, the aprotic polar solvent described in step (1) includes N, N- diformazan
Base Methanamide, DMAC N,N' dimethyl acetamide or N-Methyl pyrrolidone.
According to the preferred embodiment of the present invention, the acetic anhydride described in step (2) is 10 with the mol ratio of aromatic dianhydride:1,
Described pyridine is 1 with the mol ratio of acetic anhydride:2.
According to the preferred embodiment of the present invention, the drying described in step (2) is to be dried at room temperature for first to remove
Ethanol, then 5-10h is dried at 50-250 DEG C.
In step (2), the consumption of ethanol is not required, in the preferred embodiment of the present invention, ethanol and step
(2) mass ratio of the reaction products therefrom obtaining is 8-10:1.
According to the preferred embodiment of the present invention, described aromatic dianhydride includes 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, equal benzene
Tetracarboxylic acid dianhydride or 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids；
Described aromatic diamines include the diphenylamines with bridge formation atom, and preferably described aromatic diamines include 4,4'- bis- amido two
Double [4- (the 4- aminobenzene oxygen of phenylate, MDA, 2,2- bis- [4- (4- amino-benzene oxygen) phenyl] propane, 2,2-
Base) phenyl] double (3- amino-4-hydroxylphenyl) HFC-236fa of HFC-236fa or 2,2-.
Above-mentioned 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, the molecular formula of 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids are respectively as following formula
(1), shown in (2)：
Above-mentioned 4,4'- diaminodiphenyl ether, MDA, 2,2- bis- [4- (4- amino-benzene oxygen) phenyl] propane,
Double (3- amino-4-hydroxylphenyl) HFC-236fa of double [4- (4- amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, 2,2- point
Minor is respectively as shown in following formula (3), (4), (5), (6), (7)：
According to the preferred embodiment of the present invention, the preparation method of described polyimide hollow fiber gas separation membrane includes
Following steps：
Prepare casting solution using described polyimides to prepare in polyimides by dry-wetting phase conversion method through spinning nozzle
Hollow fiber gas separation membrane.
According to the preferred embodiment of the present invention, described spinning temperature is 15-70 DEG C.
According to the preferred embodiment of the present invention, described dry-wetting phase conversion method coagulating bath adopts water-bath, and bath temperature is
0-30℃.
According to the preferred embodiment of the present invention, described prepare the spinning that polyimide hollow fiber gas separation membrane is used
The concentration mass fraction of liquid is 20-45%, and described solvent includes DMF, N,N-dimethylacetamide
Or the combination of one or more of N-Methyl pyrrolidone.
According to the preferred embodiment of the present invention, described prepare the spinning that polyimide hollow fiber gas separation membrane is used
Core liquid is included by N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone or methanol and water group
The core liquid becoming.
According to the preferred embodiment of the present invention, described DMF, N,N-dimethylacetamide, N-
Methyl pyrrolidone or methanol are 20 with the mass ratio of water:80-80:20.
According to the preferred embodiment of the present invention, above-mentioned logical through spinning nozzle using described polyimides preparation casting solution
Overdrying-wetting phase conversion method is prepared polyimide hollow fiber gas separation membrane and is specifically included following steps：
At 50-70 DEG C, with DMF, N,N-dimethylacetamide or N-Methyl pyrrolidone
The spinning liquid being combined as aprotic polar solvent preparation polyimides of one or more, stirs, standing and defoaming
More than 6h, obtains the spinning liquid after deaeration；
Prepare core liquid；
With pump, the spinning liquid after deaeration and core liquid are injected spinning nozzle, using dry air as spinning motive force,
Through spinning nozzle, form as-spun fibre, using water as the first coagulating bath film-forming, water temperature controls at 0-30 DEG C；
Subsequently this film is soaked in water 12-48h except residual solvent in striping after, then at the second gelation (water or glycerol)
In carry out 12-24h being dried under solvent exchange, room temperature after, obtain described polyimide hollow fiber gas separation membrane.
As a comparison, present invention also offers a kind of preparation method of polyimides Flat Membrane, this preparation method include with
Lower step：
Under step a, inert atmosphere, aromatic diamines and aromatic dianhydride are dissolved in aprotic polar solvent, and at -30 DEG C
React 4-24h to room temperature, obtain polyamic acid solution；
Step b, by the polyamic acid solution obtaining dilute, with low concentration, (5-15wt%, with the gross mass of solution
For 100% meter) spread under clean glass plate, carry out hot-imide or chemical imidization at different temperatures
Process.Demoulding, obtains polyimides Flat Membrane, and the thickness of this film is 20-100 μm；Above-mentioned hot-imide anti-
It is relevant with the glass transition temperature of the structure of the polyimides preparing and polyimides to answer temperature, art technology
Personnel can select suitably hot acid imide according to the structure of the polyimides preparing and its glass transition temperature
Change reaction temperature.
In the preferred embodiment of the present invention, above-mentioned steps a can follow the steps below：Protect in noble gases
Under shield, in round-bottomed flask, add a certain amount of aprotic polar solvent, add aromatic diamine monomers after deoxygenation, stir
Mix to being completely dissolved, bath on the rocks, make system temperature be down to 0 DEG C；Add the aromatic dianhydride monomer of equimolar ratio, make anti-
Answer thing concentration to control between 20-40wt%, react 4-24 hour at 0 DEG C, obtain polyamic acid solution；
Present invention also offers the modification that the method for modifying of above-mentioned polyimide hollow fiber gas separation membrane prepares
Polyimide hollow fiber gas separation membrane.
Present invention also offers above-mentioned modified polyimide Ho llow fiber membrane for gas separation CO in removing biogas2Should
With.
The modified polyimide Ho llow fiber membrane for gas separation that the present invention provides has excellent thermostability, resistance to organic molten
Agent performance and excellent mechanical properties；The modified polyimide Ho llow fiber membrane for gas separation of the present invention is used for removing biogas
Middle CO2, it is to CO2/CH4Mixed gas have good separating effect, that is, have high selectivity and breathability,
CO can be increased substantially2The infiltration coefficient of gas.
Specific embodiment
Describe the implementation process of the present invention and the beneficial effect of generation below by way of specific embodiment in detail it is intended to help read
Reader more fully understands essence and the feature of the present invention, not as to this case can practical range restriction.
Embodiment 1
Present embodiments provide a kind of preparation method of modified polyimide Ho llow fiber membrane for gas separation, this preparation method
Comprise the following steps：
(1) preparation of polyimide material
It is passed through nitrogen in the there-necked flask being dried, add the N,N-dimethylacetamide of 60mL, under mechanical agitation
Add double (3- amino-4-hydroxylphenyl) HFC-236fa of 20.15g (55mmol) 2,2-, stir to its be completely dissolved after on the rocks
Bath, temperature of reaction system is down to 0 DEG C；Then, by the 3,3 ' -4 of 17.71g (55mmol), 4 '-benzophenone tetracid two
Acid anhydride is dividedly in some parts, and when system color is changed into crocus, adds the N,N-dimethylacetamide of 20mL.Here
At a temperature of react 6 hours, obtain polyamic acid solution.
(2) preparation method of polyimide hollow fiber gas separation membrane
Chemical method imidizate is adopted to the polyamic acid obtaining in step (1).0.55 is added in polyamic acid solution
Mol acetic anhydride and 0.275mol pyridine make polyamic acid imidizate, stir under room temperature, react 12h；Institute will be reacted
Obtain product and add sedimentation in ethanol, stirring, to guarantee to reel off raw silk from cocoons, after removing ethanol is dried, puts it into vacuum under room temperature
100 DEG C of dryings of baking oven 10 hours, obtain polyimides；
Subsequently polyimides are dissolved in DMAC N,N' dimethyl acetamide (DMAC) solvent and make mass fraction for 30%
The polyimides spinning liquid of concentration, adds it to 6h be stirred at room temperature in constant temperature spinning box, standing, deaeration 12h；
Using core liquid be methanol and water composition core liquid, wherein methanol and the mass ratio of water are 50:50.Using dry-Wet-spinning
Silk, makes film liquid form as-spun fibre after spinning nozzle at 50 DEG C, enters coagulating bath (water-bath, temperature afterwards
Spend for 20 DEG C) film-forming；Collect fiber；Soak 12h and remove residual solvent in striping in water.Afterwards by hollow
Fiber is according to carrying out solvent displacement in the second gelation.12h is dried under room temperature, obtains polyimide hollow fiber gas
Seperation film；
(3) preparation method of modified polyimide Ho llow fiber membrane for gas separation
Using60The polyimide hollow fiber gas separation membrane that Co- gamma-rays prepare to step (2) room temperature,
Carry out radiation modification process, irradiation dose is respectively 25kGy, 50kGy, 100kGy, 200kGy under limited oxygen condition,
Obtain the polyimide hollow fiber gas separation membrane of radiation modification.
Embodiment 2
Present embodiments provide a kind of preparation method of modified polyimide Ho llow fiber membrane for gas separation, this preparation method
Comprise the following steps：
(1) preparation of polyimide material
It is passed through nitrogen in the there-necked flask being dried, add the N,N-dimethylacetamide of 90mL, under mechanical agitation
Add 10.01g (50mmol) 4,4 '-diaminodiphenyl ether, stir and be completely dissolved rear bath on the rocks to it, by reaction system
Temperature is down to 0 DEG C；Then, 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids of 22.21g (50mmol) are dividedly in some parts,
Rinse bottleneck with 6mL DMAC N,N' dimethyl acetamide.React 12 hours at this temperature, obtain polyamic acid solution.
(2) preparation method of polyimide hollow fiber gas separation membrane
Chemical method imidizate is adopted to the polyamic acid obtaining in step (1).0.5 is added in polyamic acid solution
Mol acetic anhydride and 0.25mol pyridine make polyamic acid imidizate, stir under room temperature, react 24h；Institute will be reacted
Obtain product and add sedimentation in ethanol, stirring, to guarantee to reel off raw silk from cocoons, after removing ethanol is dried, puts it into vacuum under room temperature
120 DEG C of dryings of baking oven 10 hours, obtain polyimides；
Subsequently polyimides are dissolved in DMAC N,N' dimethyl acetamide (DMAC) solvent and make mass fraction for 25%
The polyimides spinning liquid of concentration, adds it to 6h be stirred at room temperature in constant temperature spinning box, standing, deaeration 6h；；
Using core liquid be methanol and water composition core liquid, wherein methanol and the mass ratio of water are 50:50.Using dry-Wet-spinning
Silk, makes film liquid form as-spun fibre after spinning nozzle at 30 DEG C, enters coagulating bath (water-bath, temperature afterwards
Spend for room temperature) film-forming；Collect fiber；Soak 12h and remove residual solvent in striping in water.Afterwards by hollow
Fiber is according to carrying out solvent displacement in the second gelation.24h is dried under room temperature, obtains polyimide hollow fiber gas
Seperation film；
(3) preparation method of modified polyimide Ho llow fiber membrane for gas separation
Using60The polyimide hollow fiber gas separation membrane that Co- gamma-rays prepare to step (2) room temperature,
Carry out radiation modification process, irradiation dose is respectively 25kGy, 50kGy, 100kGy, 200kGy under limited oxygen condition,
Obtain the polyimide hollow fiber gas separation membrane of radiation modification.
Comparative example 1
Present embodiments provide a kind of preparation method of modified polyimide Flat Membrane, this preparation method includes following step
Suddenly：
(1) preparation of polyimide material
It is passed through nitrogen in the there-necked flask being dried, add the N,N-dimethylacetamide of 60mL, under mechanical agitation
Add double (3- amino-4-hydroxylphenyl) HFC-236fa of 20.15g (55mmol) 2,2-, stir to its be completely dissolved after on the rocks
Bath, temperature of reaction system is down to 0 DEG C；Then, by the 3,3 ' -4 of 17.71g (55mmol), 4 '-benzophenone tetracid two
Acid anhydride is dividedly in some parts, and when system color is changed into crocus, adds the N,N-dimethylacetamide of 20mL.Here
At a temperature of react 6 hours, obtain polyamic acid solution.
(2) preparation of polyimides Flat Membrane
It is 15% that the polyamic acid solution DMAC N,N' dimethyl acetamide that step (1) is synthesized is diluted to mass fraction
Solution, is laid on clean glass plate with knifing machine afterwards；Carry out hot-imide in nitrogen charging baking oven, tool
Temperature with the time is：80 DEG C of constant temperature 1h, 120 DEG C of constant temperature 1h, 150 DEG C of constant temperature 1h, 230 DEG C of constant temperature 3h, 250 DEG C
Constant temperature 2h, 270 DEG C of constant temperature 1h；It is cooled to room temperature again, then polyimides Flat Membrane is peeled off from glass,
Obtain polyimides Flat Membrane (thickness is usually 20-80 μm)；
(3) preparation of modified polyimide Flat Membrane
Using60The polyimides Flat Membrane that Co- gamma-rays prepare to step (2) is entered under room temperature, limited oxygen condition
Row radiation modification is processed, and irradiation dose is respectively 25kGy, 50kGy, 100kGy, 200kGy, obtains irradiation and changes
The polyimides Flat Membrane of property.
In order to the speed of the various gas permeation gas separation membranes of quantitative sign, and by dissolubility and diffusion velocity
Quantification, so the infiltration coefficient of gas is diffusion coefficient and dissolubility is long-pending.
P=D × S
In formula：P is the infiltration coefficient of gas, and dimension is：cm3(STP)·cm/cm2S cmHg is it is also possible to use
Barrer represents, 1barrer=10-10cm3(STP)·cm/cm2·s·cmHg；D is diffusion coefficient, and dimension is cm2/ s,
It is usually used：10-8cm2/s；S is solubility coefficient, and dimension is cm3(STP)/cm3CmHg, is usually used：
10-3cm3(STP)/cm3·cmHg.
P is an important parameter characterizing film properties, and the another one important parameter characterizing film properties is separation
α, αA/B=PA/PB, wherein PAFor the infiltration coefficient of fast gas, PBFor the infiltration coefficient of slow gas, therefore α >=1.α
Bigger, show that the separating power of film is stronger.
Application examples 1
The polyimide hollow fiber gas separation membrane that above-described embodiment 1 prepares, modified poly- should be provided by use-case
Acid imide Ho llow fiber membrane for gas separation CO in removing biogas2Application, this application comprises the following steps：
In the polyimide hollow fiber gas separation membrane that prepared using the embodiment of the present invention 1, modified polyimide
Hollow fiber gas separation membrane (absorbed dose are 50kGy) is respectively to CH4And CO2Carry out gas-premeable experiment,
Experiment condition, temperature：30 DEG C, pressure：2 atmospheric pressure；CH can be respectively obtained by experiment4And CO2Pass through
Polyimide hollow fiber gas separation membrane and the infiltration coefficient of modified polyimide Ho llow fiber membrane for gas separation, its
In, in the case of using modified polyimide Ho llow fiber membrane for gas separation (absorbed dose are 50kGy), CO2
Infiltration coefficient (the P of gasCO2) it is 5.671barrer, CH4Infiltration coefficient (the P of gasCH4) it is 0.0654barrer,
So gas selectivity α is 86.713；In the case of using unmodified polyimide hollow fiber gas separation membrane,
CO2Infiltration coefficient (the P of gasCO2) it is 5.070barrer, CH4Infiltration coefficient (the P of gasCH4) it is 0.0786
Barrer, so gas selectivity α is 64.504.It can thus be seen that the modified polyimide that the present invention prepares
The CO of Ho llow fiber membrane for gas separation (absorbed dose are 50kGy)2/CH4Separation is larger, and unmodified
Polyimide hollow fiber gas separation membrane is compared, and the modified polyimide Ho llow fiber membrane for gas separation of the present invention (is inhaled
Receipts dosage be 50kGy) CO2/CH4Separation improves 34.43%.
Application examples 2
The polyimide hollow fiber gas separation membrane that above-described embodiment 2 prepares, modified poly- should be provided by use-case
Acid imide Ho llow fiber membrane for gas separation CO in removing biogas2Application, this application comprises the following steps：
(absorbed dose are the modified polyimide Ho llow fiber membrane for gas separation being prepared using the embodiment of the present invention 2
50kGy) to CO2Carry out gas-premeable experiment, experiment condition, temperature：30 DEG C, pressure：2 atmospheric pressure；
CO can be obtained by experiment2By unmodified polyimide hollow fiber gas separation membrane, modified polyimide
The infiltration coefficient of Ho llow fiber membrane for gas separation, wherein, (is being inhaled using modified polyimide Ho llow fiber membrane for gas separation
Receipts dosage is 50kGy) in the case of, CO2Infiltration coefficient (the P of gasCO2) it is 9.61barrer；Using not
In the case of modified polyimide Ho llow fiber membrane for gas separation, CO2Infiltration coefficient (the P of gasCO2) it is 8.60
barrer.Compared with the modified polyimide Ho llow fiber membrane for gas separation preparing with embodiment 1, embodiment 2 is made
The CO of the standby modified polyimide Ho llow fiber membrane for gas separation obtaining2Gas permeability is higher, but CO2/CO4Choosing
Selecting property declines.
Claims (10)
1. a kind of method of modifying of polyimide hollow fiber gas separation membrane, wherein, the method comprises the following steps：
Radiation modification process is carried out to polyimide hollow fiber gas separation membrane using ionizing radiation, obtains described modified place
The polyimide hollow fiber gas separation membrane of reason；
Preferably described radiation absorber amount is 15-200kGy；
It is also preferred that ionizing radiation includes gamma-rays and X-ray；More preferably described gamma-rays include60Co- gamma-rays
With137Cs- gamma-rays.
2. method according to claim 1, wherein, described irradiation is under air, limit oxygen or oxygen free condition
Carry out.
3. method according to claim 1, wherein, the preparation of described polyimides comprises the following steps：
Polyimides are prepared using aromatic diamines and aromatic dianhydride；Preferably described aromatic dianhydride and the mol ratio of aromatic diamines
For 0.9-1.5:1.
4. method according to claim 3, wherein, the preparation of described polyimides follows the steps below：
(1), under inert atmosphere, aromatic diamines and aromatic dianhydride are dissolved in aprotic polar solvent, obtain solution
A, solution A is reacted 4-24h under -30 DEG C to room temperature, obtains polyamic acid solution；
The mass concentration of described solution A is 20-30wt%；
Preferably described aprotic polar solvent includes N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or N- first
Base ketopyrrolidine；
(2), the polyamic acid solution obtaining to step (1) adds acetic anhydride and pyridine, stirs under room temperature, reaction
12-24h；Products therefrom will be reacted add in ethanol, stir to guarantee to reel off raw silk from cocoons, more after drying, obtain polyamides sub-
Amine；
Preferably described acetic anhydride is 10 with the mol ratio of aromatic dianhydride:1, described pyridine is 1 with the mol ratio of acetic anhydride:2；
It is also preferred that being dried is to be dried at room temperature for remove ethanol first, then 5-10h is dried at 50-250 DEG C.
5. the method according to claim 3 or 4, wherein, described aromatic dianhydride includes 3,3 ', 4,4 '-benzophenone
Tetracarboxylic dianhydride, pyromellitic acid anhydride or 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids；
Described aromatic diamines include the diphenylamines with bridge formation atom, and preferably described aromatic diamines include 4,4'- bis- amido two
Double [4- (the 4- aminobenzene oxygen of phenylate, MDA, 2,2- bis- [4- (4- amino-benzene oxygen) phenyl] propane, 2,2-
Base) phenyl] double (3- amino-4-hydroxylphenyl) HFC-236fa of HFC-236fa or 2,2-.
6. the method according to any one of claim 1-3, wherein, described polyimide hollow fiber gas divides
Preparation method from film comprises the following steps：
Prepare casting solution using described polyimides to prepare in polyimides by dry-wetting phase conversion method through spinning nozzle
Hollow fiber gas separation membrane；
Preferably described spinning temperature is 15-70 DEG C；
It is also preferred that dry-wetting phase conversion method coagulating bath adopts water-bath, bath temperature is 0-30 DEG C.
7. method according to claim 6, wherein, described prepares polyimide hollow fiber gas separation membrane
The concentration mass fraction of the spinning liquid used is 20-45%, and described solvent includes DMF, N, N- bis-
The combination of one or more of methylacetamide or N-Methyl pyrrolidone.
8. method according to claim 6, wherein, described prepares polyimide hollow fiber gas separation membrane
The spinning core liquid used include by N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone or
The core liquid that methanol is formed with water；
The matter of preferably N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone or methanol and water
Amount ratio is 20:80-80:20.
9. the method for modifying of the polyimide hollow fiber gas separation membrane described in any one of claim 1-8 is prepared into
The modified polyimide Ho llow fiber membrane for gas separation arriving.
10. the CO in removing biogas of the modified polyimide Ho llow fiber membrane for gas separation described in claim 92's
Application.
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