CN100506363C - Preparation method of polyether sulphone ketone base gas separation carbon membrane - Google Patents
Preparation method of polyether sulphone ketone base gas separation carbon membrane Download PDFInfo
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- CN100506363C CN100506363C CNB2005102007932A CN200510200793A CN100506363C CN 100506363 C CN100506363 C CN 100506363C CN B2005102007932 A CNB2005102007932 A CN B2005102007932A CN 200510200793 A CN200510200793 A CN 200510200793A CN 100506363 C CN100506363 C CN 100506363C
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- carbon membrane
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Abstract
A poly (ether-sulfone-ketone) based carbon membrane for separating gas is prepared through providing said poly (ether-sulfone-ketone) as precursor, preparing filming liquid, preparing polymer membrane, preoxidizing and carbonifying.
Description
Technical field
The invention belongs to the technology of preparing and the field of new of diffusion barrier, relate to the preparation method of polyether sulphone ketone base gas separation carbon membrane.
Background technology
Membrane separation technique has efficiently, and advantages such as the energy are saved in environmental protection, have obtained the progress of advancing by leaps and bounds in recent decades, now have been widely used in numerous areas such as food, biology, chemical industry, the energy, environmental protection.Gas separation membrane is the important component part of membrane science and technology, can be used for directly from air oxygen separation and nitrogen, the hydrogen from reclaim synthetic ammonia relief gas and from natural gas, remove aspect such as carbon dioxide, be considered to the third generation gas separation that has development prospect most after transformation absorption and cryogenic rectification.Raising along with people's production and living needs, the development of gas separation membrane faces two stern challenges, the first improves the gas permeability and the selectivity of film on bigger degree, it two is that gas separation membrane still can keep its good gas separating power (Koros W J, et al.J.Membr.Sci.175 (2000): 181 under rigorous environment such as HTHP
)。Though effort through numerous researchers, the performance of membrane material is greatly improved and improves, but the gas separating property of traditional organic film (permeability and selectivity) still is difficult to surmount the Robeson upper limit, under this overall background situation, the carbon membrane that had outstanding gas separating property has in the last few years attracted more and more researchers' concern (Koros W J, et al.J.Membr.Sci.175 (2000): 181).Compare with traditional organic film, carbon membrane not only has higher permeance property, also has higher heat endurance, chemical stability and mechanical strength in addition.Carbon membrane mainly is the microporous barrier for preparing by the high temperature pyrolysis polymer film.The polymer precursor that is used to prepare carbon membrane mainly contains polyimides (Suda, et al, J.Phys.Chem.B101 (1997): 1988), polyvinylidene chloride (Centeno, etal, Carbon, 38 (2000): 1067), poly furfuryl alcohol (Shiflett, et al, Science.285 (1999): 1902), polyacrylonitrile (Ismail, et al, J.Membr.Sci.213 (2003): 285), phenolic resins (Centeno, etal, 45) J.Membr.Sci.228 (2004): material such as wherein is that the carbon membrane of presoma preparation has best gas separating power with the polyimides, but its expensive is not very desirable and adopt the carbon membrane gas separating power of other presoma preparation; Traditional in addition general more complicated of carbon membrane preparation technology, usually need to rely on rear oxidation, back pyrolysis, chemical vapour desposition methods such as (CVD) and modify processing (SaufiS.M. in order to obtain having higher gas separating property, etal, Carbon 42 (2004): 241), these problems have limited the large-scale application and the commercialization process of carbon membrane to a great extent.Therefore the persursor material of research and development with perfect gas separating property carbon membrane with improve preparation technology and will promote carbon membrane and on industrially scalable, be applied to gas early and separate.
Summary of the invention
The purpose of this invention is to provide a kind of is technology and the method that presoma prepares carbon membrane with polymer-polyethersulfone ketone material.Can obtain having higher gas permeability and separation selectivity with the method, higher heat endurance is separated carbon membrane with the gas of chemical stability.
Technical scheme of the present invention is:
(1) configuration film making solution.The carbon membrane persursor material that the present invention adopts is a kind of polymeric film material-polyethersulfone ketone, and its chemical constitution is 1:4 or 1:3 or 1:1 or 3:1 or 4:1 for sulfone ketone ratio; It is dissolved in organic solvent n-formyl sarcolysine base pyrrolidones or n-formyl sarcolysine yl acetamide or dimethyl sulfoxide (DMSO) or chloroform or the n-formyl sarcolysine base formamide, is configured to the solution of 5-20%wt, through filtering, deaeration is left standstill, and obtains film making solution.
(2) preparation polymer film.The soln using solvent evaporated method is prepared flat sheet membrane, and phase inversion prepares hollow-fibre membrane, perhaps cladding process such as infusion process, spread coating, spraying process or ultrasonic deposition method etc. at supporter (as the charcoal of sheet and tubulose, graphite, stainless steel, pottery, silicon) last preparation composite membrane.The non-solvent of preparation hollow-fibre membrane is: acetone, methyl alcohol, ethanol, propyl alcohol, water; Baking temperature is 60-150 ℃, and under this temperature constant temperature 10～48h;
(3) pre-oxidation.Is 10-300ml/min with the polymer film of preparation being connected with air mass flow, and heating rate is 0.5-5 ℃/min, and temperature is to carry out pre-oxidation 10-180min in 300-500 ℃ the heating furnace.
(4) preparation carbon membrane.Carbon membrane is made in the charing under vacuum or inert gas shielding of film after the pre-oxidation,
Or directly polymer film is put into after the first pre-oxidation of retort again under vacuum or inert gas shielding charing and made carbon membrane; The inert gas that adopts is argon gas or nitrogen, and gas flow is 5-300ml/min, and carbonization heating rate is 0.5-5 ℃/min, and charing temperature eventually is 500-1000 ℃ and is incubated 30-180min, reduces to room temperature naturally;
(5) above-mentioned process technology scheme is applicable to that also with polyimides, PEI, phenolic resin, Vingon, Kynoar, polyacrylonitrile, various cellulose, polysulfones, polyether sulfone etc. be the feedstock production carbon membrane.
Effect of the present invention and benefit are:
(1) proposes a kind of carbon membrane precursor polymer material polyethersulfone ketone of novelty, widened the range of choice of carbon membrane presoma.
(2) adopting polyethersulfone ketone is the carbon membrane persursor material, and not only its price is more cheap than polyimides, and carbon membrane prepared therefrom has and the close or higher gas separating property of the inferior case of polyamides.
(3) proposing to adopt polyethersulfone ketone is that presoma prepares the technology that gas separates carbon membrane, can omit rear oxidation, back pyrolysis, chemical vapour desposition steps such as (CVD), and this preparation technology is simple, and good reproducibility is easy to industrialization.
(4) Zhi Bei carbon membrane has higher gas permeability and selectivity, heat endurance and chemical stability, improved the production capacity of gas separation membrane technology, can be used for harsh gas lock out operation environment such as high temperature (under the nonoxidizing atmosphere condition), high pressure and chemical corrosivity, help to expand gas separation membrane The Application of Technology scope.
The specific embodiment
Be described in detail most preferred embodiment of the present invention below in conjunction with technical scheme.
Embodiment 1
Polyethersulfone ketone (sulfone ketone is than being 1:1) is dissolved in the solution that is configured to 15wt% in the n-formyl sarcolysine base pyrrolidones, and the impurity in the solution, standing and defoaming 24h are again fallen in vacuum filtration through filter cloth.Behind the knifing,, in vacuum drying oven, descend dry 24h again in 100 ℃ at 80 ℃ of dry 24h.The polymer film that obtains is put in the heating furnace, is under the 150ml/min in air mass flow, control heating rate be 3 ℃/min at 460 ℃ of pre-oxidation 60min, obtain the pre-oxidation film.Polyethersulfone ketone film after the pre-oxidation is put in the tubular type retort, and the control heating rate is 1 ℃/min, is that carbonization temperature is 500-1000 ℃ of constant temperature 60min under the 200ml/min at argon flow amount, prepares the carbon membrane that thickness is 31-40 Jing.
The gas permeability data of carbon membrane product (45 ℃ of probe temperatures) are as following table.
Embodiment 2
Polyethersulfone ketone (sulfone ketone is than being 4:1) is dissolved in the solution that is configured to 12%wt in the dimethyl sulfoxide (DMSO), and the impurity in the solution, standing and defoaming 24h are again fallen in vacuum filtration through filter cloth.Behind the knifing,, in vacuum drying oven, descend dry 24h again in 100 ℃ at 80 ℃ of dry 24h.The polymer film that obtains is put in the heating furnace, is under the 200ml/min in air mass flow, control heating rate be 1 ℃/min at 400 ℃ of pre-oxidation 160min, obtain the pre-oxidation film.Polyethersulfone ketone film after the pre-oxidation is put in the tubular type retort, and the control heating rate is 5 ℃/min, is 850 ℃ of charing 60min under the 50ml/min at nitrogen flow.The permeability of the carbon membrane for preparing under 30 ℃ is: hydrogen (H
2): 118.6Barrer (1Barrer=10
-10Cm
3(STP) cmcm
-2.s
-1.CmHg
-1), carbon dioxide (CO
2): 163.9Barrer, oxygen (O
2): 26.6Barrer, nitrogen (N
2) 3.3Barrer; Selectivity is: H
2/ N
2=36.3, CO
2/ N
2=50.2, O
2/ N
2=8.1.
Embodiment 3
Polyethersulfone ketone (sulfone ketone is than being 1:4) is dissolved in the solution that is configured to 10wt% in the n-formyl sarcolysine yl acetamide, and the impurity in the solution, standing and defoaming 24h are again fallen in vacuum filtration through filter cloth.The solution of configuration is coated in by solution dipping method on the supporter of different shapes and material, in baking oven in 80 ℃ down after the dry 24h, 100 ℃ of dry 24h in vacuum drying oven again.The composite membrane that obtains is put in the heating furnace, is under the 300ml/min in air mass flow, control heating rate be 3 ℃/min at 480 ℃ of pre-oxidation 30min, obtain the pre-oxidation film.Composite membrane after the pre-oxidation is put in the tubular type retort, ... the control heating rate is 3 ℃/min, the following 750 ℃ of charing 60min of vacuum condition, retort is through cooling to room temperature naturally, and the gas permeability data of the compound carbon membrane for preparing (30 ℃ of probe temperatures) are as shown in the table:
Embodiment 4
Polyethersulfone ketone (sulfone ketone is than being 1:1) is dissolved in the solution that is configured to 10wt% in the n-formyl sarcolysine yl acetamide, and the impurity in the solution, standing and defoaming 24h are again fallen in vacuum filtration through filter cloth.The solution of configuration is adopted dry-jet wet spinning, is that gel prepares hollow-fibre membrane with water, and this film after 80 ℃ of following dry 24h, descends dry 24h in 100 ℃ again in vacuum drying oven in baking oven.The film that obtains is put in the heating furnace, is under the 30ml/min in air mass flow, control heating rate be 1 ℃/min at 350 ℃ of pre-oxidation 30min, obtain the pre-oxidation film.Composite membrane after the pre-oxidation is put in the tubular type retort, and the control heating rate is 0.5 ℃/min, is 950 ℃ of charing 180min under the 50ml/min at argon flow amount.The permeability of the carbon membrane for preparing under 30 ℃ is: hydrogen (H
2): 422.3Barrer (1Barrer=10
-10Cm
3(STP) cm cm
-2.s
-1.CmHg
-1), carbon dioxide (CO
2): 313.7Barrer, oxygen (O
2): 181.2Barrer, nitrogen (N
2) 34.6Barrer; Selectivity is: H
2/ N
2=12.2, CO
2/ N
2=9.07, O
2/ N
2=5.2.
Claims (9)
1. the preparation method of polyether sulphone ketone base gas separation carbon membrane is to be persursor material with polyether sulfone ketone, and through the preparation of polymer film, pre-oxidation and charing obtain carbon membrane; It is characterized in that:
Polyethersulfone ketone is dissolved in is configured to the 5-20wt% preparation liquid in the organic solvent;
Adopt different film-forming methods to be prepared into polymer film preparation liquid;
With the preparation polymer film at air mass flow 10-300ml/min, heating rate is 0.5-5 ℃/min, temperature is 300-500 ℃ of following pre-oxidation 10-180min;
Film after the pre-oxidation is carried out charing under vacuum or inert gas shielding, inert gas is argon gas or nitrogen, and gas flow is 5-300ml/min, and heating rate is 0.5-5 ℃/min, and charing temperature eventually is 500-1000 ℃ and is incubated 30-180min.
2. according to the preparation method of the described polyether sulphone ketone base gas separation carbon membrane of claim 1, the chemical constitution that it is characterized in that polyethersulfone ketone is that sulfone ketone is than 1:4 or 1:3 or 1:1 or 3:1 or 4:1; Used organic solvent is n-formyl sarcolysine base pyrrolidones or n-formyl sarcolysine yl acetamide or dimethyl sulfoxide (DMSO) or chloroform or n-formyl sarcolysine base formamide.
3. according to the preparation method of the described polyether sulphone ketone base gas separation carbon membrane of claim 1, it is characterized in that film making solution is through filtration, deaeration, the process of leaving standstill obtains.
4. according to the preparation method of the described polyether sulphone ketone base gas separation carbon membrane of claim 1, it is characterized in that it being to adopt solvent evaporated method to prepare flat sheet membrane, utilize phase inversion to prepare hollow-fibre membrane, perhaps utilize cladding process on porous supporting body, to prepare composite membrane.
5. according to the preparation method of the described polyether sulphone ketone base gas separation carbon membrane of claim 1, it is characterized in that the form of polymer film is: flat sheet membrane or hollow-fibre membrane or composite membrane; The non-solvent of preparation hollow-fibre membrane is: acetone or methyl alcohol or ethanol or propyl alcohol or water; Baking temperature is 60-150 ℃, and under this temperature constant temperature 10-48h.
6. according to the preparation method of the described polyether sulphone ketone base gas separation carbon membrane of claim 1, it is characterized in that directly polymer film being put into after the first pre-oxidation of retort again under vacuum or inert gas shielding charing and make carbon membrane.
7. according to the preparation method of the described polyether sulphone ketone base gas separation carbon membrane of claim 1, it is characterized in that the technology of the method is applicable to that with polyimides, PEI, phenolic resin, Vingon, Kynoar, polyacrylonitrile, various cellulose, polysulfones or polyether sulfone be the feedstock production carbon membrane.
8. according to the preparation method of the described polyether sulphone ketone base gas separation carbon membrane of claim 4, it is characterized in that cladding process is a kind of in infusion process, spread coating, spraying process or the ultrasonic deposition method.
9. according to the preparation method of the described polyether sulphone ketone base gas separation carbon membrane of claim 5, the supporter that it is characterized in that composite membrane is the charcoal of sheet or tubulose, porous graphite, porous stainless steel, porous ceramics, porous silicon a kind of.
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| CN101757859B (en) * | 2010-03-05 | 2012-05-23 | 沈阳工业大学 | Carbon membrane reactor and method for using the same |
| CN104760944B (en) * | 2015-03-16 | 2016-08-24 | 同济大学 | One one step preparation method of double-face isomeric net carbon film |
| US11007488B2 (en) * | 2016-03-16 | 2021-05-18 | Dow Global Technologies Llc | Separation of gases via carbonized vinylidene chloride copolymer gas separation membranes and processes therefor |
| CN107469640B (en) * | 2017-07-20 | 2019-11-26 | 大连理工大学 | A kind of preparation method of high gas permeability carbon membrane |
| CN108034059B (en) * | 2017-12-13 | 2020-09-29 | 大连理工大学 | Method for judging thermal crosslinking process range of thermoplastic polymer |
| CN111111465A (en) * | 2018-11-01 | 2020-05-08 | 中国科学院宁波材料技术与工程研究所 | CO (carbon monoxide)2/N2Gas separation membrane, preparation method and application thereof |
| CN109351202A (en) * | 2018-12-19 | 2019-02-19 | 安徽工业大学 | It is a kind of based on ceramic tube be the compound carbon membrane of supporter preparation method |
| CN110743389B (en) * | 2019-12-07 | 2023-03-24 | 中化泉州能源科技有限责任公司 | Carbon molecular sieve membrane and preparation method thereof |
| CN112993247A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | High-surface-capacity self-supporting hard carbon cathode and preparation and application thereof |
| CN111111466A (en) * | 2019-12-24 | 2020-05-08 | 中国科学院山西煤炭化学研究所 | Preparation method of flexible self-supporting polyacrylonitrile-based carbon film |
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