CN101480583A - Method for preparing novel polyetherimide hollow fiber film - Google Patents

Method for preparing novel polyetherimide hollow fiber film Download PDF

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CN101480583A
CN101480583A CNA2008102469954A CN200810246995A CN101480583A CN 101480583 A CN101480583 A CN 101480583A CN A2008102469954 A CNA2008102469954 A CN A2008102469954A CN 200810246995 A CN200810246995 A CN 200810246995A CN 101480583 A CN101480583 A CN 101480583A
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fibre membrane
hollow
solvent
preparing
spinning
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CN101480583B (en
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任吉中
丑树人
李晖
邓麦村
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Tianbang National Engineering Research Center Of Membrane Technology Co Ltd
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Tianbang National Engineering Research Center Of Membrane Technology Co Ltd
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Abstract

The invention relates to a novel method for preparing a polyetherimide hollow fiber membrane. Spinning solution comprises the following components in percentage by weight: 15-35 percent of polyetherimide powder, 50-75 percent of non-volatility solvent, 0-25 percent of volatile solvent and 0-15 percent of non-solvent. A dry-wet method spinning process is adopted to spin; at a temperature between 5 DEG C and 80 DEG C, the spinning solution is extruded by a nozzle; core solution adopts purified water or the mixed solution of water and solvent; a primary hollow fiber membrane passes through the distance between 0 mm and 1,000 mm in the air and enters jelly bath; the temperature of the jelly bath is controlled to be between 0 DEG C and 80 DEG C; the drafting speed rate of spinning is between 2 m/min and 50 m/min. The invention has the advantages that the prepared hollow fiber membrane has good penetrability, selectivity and pressure resisting performance and can be applied in the field of gas separation of hydrogen reclamation, air separation, carbon oxide separation, and the like.

Description

A kind of preparation method of novel polyetherimide hollow-fibre membrane
One, technical field:
The present invention relates to the preparation method of gas separation membrane, particularly the preparation method of PEI diffusion barrier.
Two, background technology:
The gas separation membrane process is a kind of new gas isolation technics that develops rapidly nearly decades, reclaims at hydrogen, and there is the application of success in fields such as air separation, carbon dioxide recovery.
Polyimides is high temperature resistant, the anti-solvent of a class, the high strength of chemicals-resistant, high performance material.Aromatic polyimide is polymerized by aromatic series tetracarboxylic dianhydride monomer and the diamine monomer with aromatic structure, and the performance of material is determined jointly that by two kinds of monomers polyimides is showing higher selection permeability aspect the gas separation.In general, its selectivity of the material of good penetrability is relatively poor, and vice versa, has the selection problem to membrane material this moment.Under the present working condition, often be difficult to directly obtain having the doughnut gas separation membrane of fine and close epidermal area, all need to fill up blemish, therefore can reduce the selectivity of hollow-fibre membrane with coating material.Obtain having higher optionally hollow-fibre membrane in order to ensure, it is higher to choose the desirable coefficient of selecting, but the lower slightly material of infiltration coefficient is as material of preparing.
Chinese invention patent 91105349.2 has been reported the method for preparing the polyimides flat sheet membrane, and the infiltration coefficient of its film and selectivity are all on the low side, and flat sheet membrane is used for gas and separates many shortcomings are arranged, and little as the filling area, floor space is big, withstand voltage properties difference etc.The polyimides hollow-fibre membrane of Chinese invention patent 98113914.0 preparations, its infiltration coefficient and permeation flux are on the low side, compare with the polysulfone hollow fibre gas separation membrane, do not have advantage on the performance.
Hydrogen at refinery gas, synthetic ammonia relief gas reclaims, and natural gas removes in the process such as carbon dioxide, and operating pressure is in the mesohigh scope, and general several MPa are to tens MPa, and this withstand voltage properties to hollow-fibre membrane has higher requirements.The diameter of hollow-fibre membrane can not be too big on the one hand; The supporting layer structure of hollow-fibre membrane will be avoided the appearance of macropore on the other hand.And present production technology adopts PEI to make hollow-fibre membrane to be difficult to realize.
Summary of the invention:
The object of the invention is to overcome existing not enough problem, and a kind of preparation method of novel polyetherimide hollow-fibre membrane is provided, and the technology uniqueness is easy to operate, the efficient height, and the PEI hollow-fibre membrane of producing is used for the gas separation field, the separating effect excellence.
The present invention is that the technical scheme that is adopted that achieves the above object is: a kind of preparation method of novel polyetherimide hollow-fibre membrane, and its preparation process is as follows:
It is the non-volatile solvents of 15-35% PEI powder, 50-75%, the volatile solvent of 0-25%, the non-solvent of 0-15% that spinning solution is formed mass percent; Adopt the spinning of dry-wet spinning technology, under 5-80 ℃ temperature, spinning solution is extruded by shower nozzle, and core liquid adopts the mixed liquor of pure water or water and solvent; Nascent hollow-fibre membrane enters coagulation bath after the process 0-1000mm distance in air; The coagulation bath temperature is controlled at 0-80 ℃; Spinning drafting rate 2-50m/min.
Its structural formula of described polyetherimide material is:
Wherein: A can be-O-,
Figure A200810246995D00072
Or
Figure A200810246995D00073
Deng; Z can be
Figure A200810246995D00074
(R=H, CH 3, OCH 3),
Figure A200810246995D00075
(R=H, CH 3, OCH 3),
Figure A200810246995D00076
(R=H, CH 3, OCH 3, B=-O-,-CH 2-,-CO-,-SO 2-,
Figure A200810246995D00077
Or
Figure A200810246995D00078
Its structural formula of the preferred polyetherimide material of described polyetherimide material is:
Figure A200810246995D00079
Or
Figure A200810246995D000710
Described non-volatile solvents comprises N-methyl pyrrolidone, N, dinethylformamide, N, N-dimethylacetylamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton or N-formylpiperidine etc.
Described non-volatile solvents comprises mixed solvent, gamma-butyrolacton and N-methyl pyrrolidone, N, dinethylformamide, N, the mixture of N-dimethylacetylamide, dimethyl sulfoxide (DMSO) or N-formylpiperidine, the mass percent 0-80% of gamma-butyrolacton in the mixed solvent.
Described volatile solvent adopts oxolane, acetone or chloroform etc.;
Described non-solvent adopts water, ethanol, ethylene glycol, propionic acid, butanols or polyethylene glycol etc.
Described core liquid is pure water or N-methyl pyrrolidone, N, dinethylformamide, N, and the aqueous solution of N-dimethylacetylamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton or N-formylpiperidine, concentration is 1-95%.
Described coagulation bath is a pure water.
Described recycle silicon rubber coating behind the hollow-fibre membrane, coating concentration 0.5-5%, 10-60 ℃ of the coating temperature of making.
The concrete advantage of the present invention is as follows:
1, to adopt high performance PEI be material of preparing in the present invention, and the doughnut gas separation membrane that obtains has the good penetration selectivity.This polyimides is to H 2/ N 2, H 2/ CH 4, CO 2/ CH 4, CO 2/ N 2, O 2/ N 2Has higher ideal separation factor etc. system.
2, different solvent and non-solvent have regulating and controlling effect to the structure of hollow-fibre membrane.The present invention adopts the interaction power between different solvents, non-solvent and the gel there are differences, regulate the kind and the proportioning of solvent and non-solvent, the regulation and control membrane structure, the development of autotelic obstruction finger-like pore and big cavity structure, thereby obtain sponge structure is main hollow-fibre membrane, has good withstand voltage properties.The hollow-fibre membrane of the present invention's preparation shows that after tested in the 0.5-5MPa pressure limit, permeability and selectivity are basicly stable.
3, the volatile solvent of the present invention's employing can be regulated hollow-fibre membrane epidermal area structure.The adding of volatile solvent in the spinning solution can reduce the defective on hollow-fibre membrane surface, regulates skin thickness by addition, thus the hollow-fibre membrane of the high selectivity of obtaining and high osmosis.
Four, the specific embodiment:
Below in conjunction with specific embodiment the present invention is described in further detail, but the invention is not restricted to specific embodiment.
Embodiment 1:
Structure is
Figure A200810246995D00091
PEI powder 1kg adds in 1.2kgN-methyl pyrrolidone, 1.2kg gamma-butyrolacton, 200g oxolane, the 400g alcohol mixed solvent, and 40 ℃ add thermal agitation, forms transparent and homogeneous solution.Solution is pressed into the deaeration jar, the vacuum standing and defoaming.Adopt the spinning of dry-wet spinning technology, spinning solution is extruded by shower nozzle, and adopting pure water is core liquid; Nascent hollow-fibre membrane enters coagulation bath through behind the 100mm in air.With after spinning wheel and collecting, in tank, remove residual solvent, 1 week the back take out in 80 ℃ of baking ovens dry 5 hours.
Comparative example 1:
Embodiment 1 resulting hollow-fibre membrane is used silicone rubber coating.
Embodiment 2:
Structure is PEI powder 1kg adds in 1.2kgN-methyl pyrrolidone, 1.2kg gamma-butyrolacton, 200g oxolane, the 400g alcohol mixed solvent, and 40 ℃ add thermal agitation, forms transparent and homogeneous solution.Solution is pressed into the deaeration jar, the vacuum standing and defoaming.Adopt the spinning of dry-wet spinning technology, spinning solution is extruded by shower nozzle, and adopting pure water is core liquid; Nascent hollow-fibre membrane enters coagulation bath through behind the 10mm in air.After spinning the wheel collection, in tank, remove residual solvent, the back taking-up of 1 week after dry 5 hours, is used silicone rubber coating in 80 ℃ of baking ovens.
Embodiment 3:
Structure is
Figure A200810246995D00093
PEI powder 1kg adds in 1kgN-methyl pyrrolidone, 1.8kg gamma-butyrolacton, the 200g oxolane bonding solvent, and 40 ℃ add thermal agitation, forms transparent and homogeneous solution.Solution is pressed into the deaeration jar, the vacuum standing and defoaming.Adopt the spinning of dry-wet spinning technology, spinning solution is extruded by shower nozzle, and adopting pure water is core liquid; Nascent hollow-fibre membrane enters coagulation bath through behind the 10mm in air.After spinning the wheel collection, in tank, remove residual solvent, the back taking-up of 1 week after dry 5 hours, is used silicone rubber coating in 80 ℃ of baking ovens.
Embodiment 4:
Structure is
Figure A200810246995D00101
PEI powder 1kg adds in 1kgN-methyl pyrrolidone, 1.8kg gamma-butyrolacton, the 200g oxolane mixed solvent, and 40 ℃ add thermal agitation, forms transparent and homogeneous solution.Solution is pressed into the deaeration jar, the vacuum standing and defoaming.Adopt the spinning of dry-wet spinning technology, spinning solution is extruded by shower nozzle, and adopting the aqueous solution of 90wt%N-methyl pyrrolidone is core liquid; Nascent hollow-fibre membrane enters coagulation bath through behind the 10mm in air.After spinning the wheel collection, in tank, remove residual solvent, the back taking-up of 1 week after dry 5 hours, is used silicone rubber coating in 80 ℃ of baking ovens.
Embodiment 5:
Structure is
Figure A200810246995D00102
PEI powder 1kg adds 1kgN-methyl pyrrolidone, 2kg gamma-butyrolacton, and 40 ℃ add thermal agitation, forms transparent and homogeneous solution.Solution is pressed into the deaeration jar, the vacuum standing and defoaming.Adopt the spinning of dry-wet spinning technology, spinning solution is extruded by shower nozzle, and adopting the N-methyl pyrrolidone aqueous solution of 90wt% is core liquid; Nascent hollow-fibre membrane enters coagulation bath through behind the 10mm in air.After spinning the wheel collection, in tank, remove residual solvent, the back taking-up of 1 week after dry 5 hours, is used silicone rubber coating in 80 ℃ of baking ovens.
The performance of the made film of embodiment 1-5 sees the following form:
Figure A200810246995D00111
Embodiment 6
Structure is
Figure A200810246995D00112
PEI powder 2.4kg adds the 3.6kgN-methyl pyrrolidone, the 2.0kg gamma-butyrolacton, and 70 ℃ add thermal agitation, form transparent and homogeneous solution, solution are pressed into the deaeration jar, the vacuum standing and defoaming.Adopt the spinning of dry-wet spinning technology, spinning solution is extruded by shower nozzle, and adopting pure water is core liquid; Nascent hollow-fibre membrane enters coagulation bath through behind the 50mm in air.After spinning the wheel collection, in tank, remove residual solvent, the back taking-up of 1 week after dry 5 hours, is used silicone rubber coating in 70 ℃ of baking ovens.
Embodiment 7
Structure is
Figure A200810246995D00121
PEI powder 1.68kg adds 2.4kg N, the N-dimethylacetylamide, and the 1.5kg gamma-butyrolacton, 0.42kg acetone, 40 ℃ add thermal agitation, form transparent and homogeneous solution, solution are pressed into the deaeration jar, the vacuum standing and defoaming.Adopt the spinning of dry-wet spinning technology, spinning solution is extruded by shower nozzle, and adopting pure water is core liquid; Nascent hollow-fibre membrane enters coagulation bath through behind the 20mm in air.After spinning the wheel collection, in tank, remove residual solvent, the back taking-up of 1 week after dry 5 hours, is used silicone rubber coating in 70 ℃ of baking ovens.
The performance of embodiment 6,7 made films sees the following form:
Figure A200810246995D00122

Claims (10)

1, a kind of preparation method of novel polyetherimide hollow-fibre membrane is characterized in that: it is the non-volatile solvents of 15-35% PEI powder, 50-75%, the volatile solvent of 0-25%, the non-solvent of 0-15% that spinning solution is formed mass percent; Adopt the spinning of dry-wet spinning technology, under 5-80 ℃ temperature, spinning solution is extruded by shower nozzle, and core liquid adopts the aqueous solution of pure water or solvent; Nascent hollow-fibre membrane enters coagulation bath after the process 0-1000mm distance in air; The coagulation bath temperature is controlled at 0-80 ℃; Spinning drafting rate 2-50m/min.
2, the method for preparing the PEI hollow-fibre membrane according to claim 1 is characterized in that: its a kind of in the following structural formula of the polyetherimide material in the spinning solution:
Figure A200810246995C00021
Wherein: A is-O-or
Figure A200810246995C00022
Or
Figure A200810246995C00023
Z is (R=H, CH 3, OCH 3) or
Figure A200810246995C00025
(R=H, CH 3, OCH 3) or
Figure A200810246995C00026
(R=H, CH 3, OCH 3B=-O-,-CH 2-,-CO-,-SO 2-, ) or Or
Figure A200810246995C00029
3, the method for preparing the PEI hollow-fibre membrane according to claim 1 is characterized in that: the polyetherimide material of the preferred following structural formula of polyetherimide material:
Figure A200810246995C00031
Or
Figure A200810246995C00032
4, according to the arbitrary described method for preparing the PEI hollow-fibre membrane of claim 1-3, it is characterized in that: non-volatile solvents adopts N-methyl pyrrolidone, N, dinethylformamide, N, N-dimethylacetylamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton or N-formylpiperidine.
5, according to the arbitrary described method for preparing the PEI hollow-fibre membrane of claim 1-3, it is characterized in that: non-volatile solvents adopts mixed solvent, be gamma-butyrolacton and N-methyl pyrrolidone, N, dinethylformamide, N, the mixture of N-dimethylacetylamide, dimethyl sulfoxide (DMSO) or N-formylpiperidine, the mass percent 0-80% of gamma-butyrolacton in the mixed solvent.
6, according to the arbitrary described method for preparing the PEI hollow-fibre membrane of claim 1-3, it is characterized in that: volatile solvent adopts oxolane, acetone or chloroform.
7, according to the arbitrary described method for preparing the PEI hollow-fibre membrane of claim 1-3, it is characterized in that: non-solvent adopts water, ethanol, ethylene glycol, propionic acid, butanols or polyethylene glycol.
8, according to the arbitrary described method for preparing the PEI hollow-fibre membrane of claim 1-3, it is characterized in that: make recycle silicon rubber coating behind the hollow-fibre membrane, coating concentration 0.5-5%, 10-60 ℃ of coating temperature.
9, according to the arbitrary described method for preparing the PEI hollow-fibre membrane of claim 1-3, it is characterized in that: core liquid is pure water or N-methyl pyrrolidone, N, dinethylformamide, N, the aqueous solution of N-dimethylacetylamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton or N-formylpiperidine, concentration are 1-95%.
10, according to the arbitrary described method for preparing the PEI hollow-fibre membrane of claim 1-3, it is characterized in that: coagulation bath is a pure water.
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101992033A (en) * 2009-08-28 2011-03-30 陈克 Method for preparing polyimide hollow fiber pervaporation membrane and application thereof
CN102565282A (en) * 2011-12-14 2012-07-11 天邦膜技术国家工程研究中心有限责任公司 Sample evaluation method for hollow fiber membrane silk
CN103084078A (en) * 2012-12-17 2013-05-08 中国科学院大连化学物理研究所 Mixed matrix membrane of polyetherimide and fumed silicon dioxide, and preparation and application thereof
CN104321132A (en) * 2012-03-30 2015-01-28 三菱丽阳株式会社 Composite hollow fiber membrane and hollow fiber membrane module
CN104994940A (en) * 2013-02-27 2015-10-21 Nok株式会社 Method of manufacturing hollow fiber carbon membrane
CN106390780A (en) * 2015-07-29 2017-02-15 北京市射线应用研究中心 Modified polyimide hollow fiber gas separation membrane, modification method and applications thereof
CN108532025A (en) * 2018-05-05 2018-09-14 程桂平 A method of preparing composite fibre
CN110404423A (en) * 2019-08-16 2019-11-05 中国科学院大连化学物理研究所 A kind of high-performance polyimide hollow-fibre membrane and the preparation method and application thereof
CN113856485A (en) * 2021-11-05 2021-12-31 无锡达魔材料科技有限公司 Preparation process of hollow fiber nitrogen-rich membrane with dense membrane wall inner edge
CN114618321A (en) * 2020-12-11 2022-06-14 中国科学院大连化学物理研究所 Hollow fiber membrane, preparation and application in hydraulic oil degassing

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US5928410A (en) * 1997-12-09 1999-07-27 Texaco Inc. Supported gas separation membrane, process for its manufacture and use of the membrane in the separation of gases

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101992033A (en) * 2009-08-28 2011-03-30 陈克 Method for preparing polyimide hollow fiber pervaporation membrane and application thereof
CN102565282B (en) * 2011-12-14 2015-07-22 天邦膜技术国家工程研究中心有限责任公司 Sample evaluation method for hollow fiber membrane silk
CN102565282A (en) * 2011-12-14 2012-07-11 天邦膜技术国家工程研究中心有限责任公司 Sample evaluation method for hollow fiber membrane silk
CN104321132A (en) * 2012-03-30 2015-01-28 三菱丽阳株式会社 Composite hollow fiber membrane and hollow fiber membrane module
CN103084078B (en) * 2012-12-17 2016-06-01 中国科学院大连化学物理研究所 A kind of polyetherimide and aerosil mixed substrate membrane containing nano-grade molecular sieve, preparations and applicatio
CN103084078A (en) * 2012-12-17 2013-05-08 中国科学院大连化学物理研究所 Mixed matrix membrane of polyetherimide and fumed silicon dioxide, and preparation and application thereof
CN104994940A (en) * 2013-02-27 2015-10-21 Nok株式会社 Method of manufacturing hollow fiber carbon membrane
CN104994940B (en) * 2013-02-27 2017-03-22 Nok株式会社 Method of manufacturing hollow fiber carbon membrane
CN106390780A (en) * 2015-07-29 2017-02-15 北京市射线应用研究中心 Modified polyimide hollow fiber gas separation membrane, modification method and applications thereof
CN108532025A (en) * 2018-05-05 2018-09-14 程桂平 A method of preparing composite fibre
CN110404423A (en) * 2019-08-16 2019-11-05 中国科学院大连化学物理研究所 A kind of high-performance polyimide hollow-fibre membrane and the preparation method and application thereof
CN114618321A (en) * 2020-12-11 2022-06-14 中国科学院大连化学物理研究所 Hollow fiber membrane, preparation and application in hydraulic oil degassing
CN113856485A (en) * 2021-11-05 2021-12-31 无锡达魔材料科技有限公司 Preparation process of hollow fiber nitrogen-rich membrane with dense membrane wall inner edge
CN113856485B (en) * 2021-11-05 2024-01-26 无锡达魔材料科技有限公司 Preparation method of hollow fiber nitrogen-rich membrane for gas separation with compact inner edge of membrane wall

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