CN110465207A - The preparation facilities and its method of a kind of Novel hollow fiber gas separation membrane and application - Google Patents
The preparation facilities and its method of a kind of Novel hollow fiber gas separation membrane and application Download PDFInfo
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- CN110465207A CN110465207A CN201910866683.1A CN201910866683A CN110465207A CN 110465207 A CN110465207 A CN 110465207A CN 201910866683 A CN201910866683 A CN 201910866683A CN 110465207 A CN110465207 A CN 110465207A
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- 238000000034 method Methods 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 60
- 239000012528 membrane Substances 0.000 title claims abstract description 51
- 238000000926 separation method Methods 0.000 title claims abstract description 45
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 85
- 239000007789 gas Substances 0.000 claims abstract description 38
- 239000002904 solvent Substances 0.000 claims abstract description 36
- 239000000835 fiber Substances 0.000 claims abstract description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052734 helium Inorganic materials 0.000 claims abstract description 4
- 239000001307 helium Substances 0.000 claims abstract description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims description 72
- 238000007711 solidification Methods 0.000 claims description 56
- 230000008023 solidification Effects 0.000 claims description 55
- 239000007788 liquid Substances 0.000 claims description 36
- 238000006073 displacement reaction Methods 0.000 claims description 35
- 238000005345 coagulation Methods 0.000 claims description 22
- 230000015271 coagulation Effects 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000007921 spray Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 16
- 238000005491 wire drawing Methods 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 12
- 230000007704 transition Effects 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229920002379 silicone rubber Polymers 0.000 claims description 9
- 239000004945 silicone rubber Substances 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004697 Polyetherimide Substances 0.000 claims description 6
- 229920001601 polyetherimide Polymers 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229920002492 poly(sulfone) Polymers 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000004513 sizing Methods 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 235000012489 doughnuts Nutrition 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 1
- 239000004695 Polyether sulfone Substances 0.000 claims 1
- 239000004743 Polypropylene Substances 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims 1
- 235000000396 iron Nutrition 0.000 claims 1
- 229920006393 polyether sulfone Polymers 0.000 claims 1
- -1 polypropylene Polymers 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 235000011164 potassium chloride Nutrition 0.000 claims 1
- 239000001103 potassium chloride Substances 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000008859 change Effects 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 description 14
- 238000001723 curing Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 8
- 238000009987 spinning Methods 0.000 description 5
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004033 diameter control Methods 0.000 description 1
- 238000011438 discrete method Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0083—Thermal after-treatment
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
-
- 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
- B01D69/08—Hollow fibre membranes
-
- 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
- B01D69/08—Hollow fibre membranes
- B01D69/085—Details relating to the spinneret
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention proposes preparation facilities and its method and the application of a kind of novel high-performance hollow-fibre membrane, the exchange of solvent of film wire, dryness finalization, film wire coating process and curing process is integrated in one apparatus, form continuous hollow tunica fibrosa preparation process, change the hollow fiber film thread preparation process of previous segmented, improve the stability and safety of film wire preparation, shorten film wire preparation time simultaneously, significantly improves the production efficiency of film wire.Prepared by the method hollow-fibre membrane can be used for gas with various separation, and such as oxygen and nitrogen separation, hydrogen and nitrogen separation, hydrogen and carbon dioxide separation, carbon dioxide and methane separation, helium and nitrogen separation and xenon are separated with air.
Description
Technical field
The invention belongs to technical field of membrane separation, be related to a kind of Novel hollow fiber gas separation membrane preparation facilities and its
Method and application.
Background technique
Membrane separation technique is a kind of novel isolation technics, and after decades of development, gas membrane Seperation Technology is with efficient
Energy conservation, it is easy to operate, it is environmentally protective the features such as be increasingly valued by people.
The preparation method of industrial widely used Ho llow fiber membrane for gas separation is phase transition method at present.Different production
The production technology that manufacturer prepares hollow-fibre membrane belongs to know-how.It can see hollow-fibre membrane in document from publishing
Preparation method is segmented (shown in Fig. 2), and specific process flow is as follows:
First stage: by 25%~40% high molecular material, 35%~60% mixed solvent, 0~5% inorganic salts
It is added in material-compound tank, stirred 48 hours in 50~100 DEG C of conditions or more, form uniform Polymer Solution.Solution passes through 48
Hour or more vacuum defoamation and curing, formed film liquid.After film liquid and inner gel agent pass through porous spray plate, into the first outer gel
Bath, usually water, occurs phase transition process, forms nascent state hollow fiber film thread, and film wire is collected into wheel.
Second stage: it after film wire is collected into wheel, impregnates in the sink, is used for exchange of solvent 5 days~10 days, then by film wire
It is put into baking oven, sizing is dried.
Phase III: the coating of film wire.There is a small amount of " lack using the surface of the hollow fiber film thread of phase transition method preparation
Fall into ", it needs to repair " defect " on film wire surface using surface coating technique.
Tens of thousands of and hundreds of thousands root film wire collection are bundled together to form film core by coating procedure, are placed on coated pipe, coating solution
Coated pipe is entered by feed inlet, each film wire in film core will be immersed in coating solution, completed to carry out coating process, such as be schemed
Shown in 3.It is first contacted with the film wire on the outside of film core in coated pipe floating coat liquid, coating solution gradually penetrates into film core inner, film in-core
The film wire in portion could be contacted with coating solution, complete the coating of film wire.The shortcomings that this coating process is that film wire coating procedure is uneven
It is even.
Part IV: the solidification of coating material.Film wire after coating is put to the solidification for carrying out silicon rubber in an oven.It will be several
The film core of ten thousand and hundreds of thousands root film wire, which is put into baking oven, to be solidified, as shown in figure 4, the film wire on the outside of film core is heated
Situation is different with the heated situation of the film wire in film core inner, and this curing method causes the film wire in film core different location
Heated situation is different, and then causes membrane module performance unstable.
By 4 stages above, hollow fiber film thread preparation is completed.Using segmented, film wire preparation process prepares hollow fibre
Film wire is tieed up, since each preparation process is independent, leads to film wire long preparation period, the connection of each preparatory phase needs to pass through craft
Process is completed, and in coating procedure and solidification process, there are inhomogeneities, directly affect the stability of membrane module.
Summary of the invention
Based on background above technology, the present invention proposes the preparation facilities and method of a kind of novel hollow-fibre membrane, utilizes
One-step method prepares hollow fiber film thread, effectively connects the spinning technique of film wire, drying process, coating process with curing process
Get up, reduce film wire manufacturing cycle, reduce Manual operation link, most importantly can be improved film wire coating procedure and solidified
The uniformity and stability of journey, and then improve membrane module performance.In the coating procedure of integral hollow fiber film wire preparation process
Middle film wire is the contact coating solution in the form of single film wire, guarantees that coating solution can be coated uniformly on film wire surface；Simultaneously solid
It during changing is entered in solidification case in the form of single film wire, guarantees the cured uniformity of film wire and stability, Jin Erti
The performance of high membrane module.
Specifically adopt the following technical scheme that:
One aspect of the present invention provides a kind of Ho llow fiber membrane for gas separation preparation facilities, and described device successively includes porous spray
Plate, the first outer gel slot, the second outer gel slot, displacement slot, the first tension controller, the first baking oven, coating slot, the second tension control
Device, the second baking oven, solidification case, third tension controller and film wire collecting wheel processed.It the first gel slot, the second gel slot and sets
It changes slot and is provided with driving wheel, the driving wheel is used to draw the film wire formed in gel slot and displacement slot, and first baking oven applies
It is equipped with guide wheel in layer pipe, the second baking oven and solidification case, the speed of first baking oven and coated pipe guide wheel is by the first tension force
The speed of the control of device, second baking oven and solidification case guide wheel is controlled by the second tension controller, and the film wire collects wheel speed
Control of the degree by third tension controller.
Based on above technical scheme, it is preferred that described device further include material-compound tank, Debubbling tank, inner gel tank, gear pump and
Metering pump, the solution of the material-compound tank are delivered to porous spray plate after Debubbling tank, by gear pump；The solution of the inner gel tank
Porous spray plate is delivered to by metering pump.
Another aspect of the present invention proposes a kind of preparation method of hollow-fibre membrane: using above-mentioned device, including walks as follows
It is rapid:
(1) by high molecular material, solvent A, inorganic salts are added in material-compound tank, and it is small that 48 are stirred under the conditions of 50 DEG C -100 DEG C
When more than, until high molecular material is completely dissolved, form uniform Polymer Solution；The high molecular material, solvent A and inorganic
The mass ratio of salt are as follows: 25-40:35-75:0.01-5.
(2) Polymer Solution enters Debubbling tank under pressure, by vacuum defoamations in 72-120 hours and ripe
Change, forms film liquid；
(3) film liquid and inner gel liquid are respectively under the conveying of gear pump and metering pump, by porous spray plate, into
One outer gel slot, the first outer gel slot is usually water, but is not limited to water, film wire the first outer gel slot residence time be 5 seconds-
30 seconds, phase transition occurred for film liquid, formed nascent state hollow fiber film thread；Film wire enters the second outer gel slot, the second outer gel slot
Water is usually selected, but is not limited to water, carries out exchange of solvent, by the exchange of solvent in film wire into water, film wire is in the second outer coagulation bath
Residence time be -300 seconds 30 seconds, make the content of solvent in film wire lower than 1%；Film wire enters displacement bath, displacement bath usually choosing
Select the alcohol reagents such as ethyl alcohol, propyl alcohol, isobutanol, it is therefore an objective to the moisture in film wire is replaced as alcohols, film wire is in displacement bath
Residence time is -240 seconds 30 seconds, guarantees that the moisture content in film wire is lower than 2%；Before film wire enters the first baking oven, setting first
A tenslator, film wire enter the first baking oven, and the temperature of the first baking oven is controlled at 90 DEG C -150 DEG C, it is therefore an objective to be made in film wire
Alcohols, a small amount of water and solvent volatilization；Film wire enters coating slot and carries out surface reconditioning, and coating slot has collet, and temperature is controlled 5
DEG C -30 DEG C, the coating solution in coating slot is the silicone rubber solution of 0.1%-10%, solvent be pentane, normal hexane, petroleum ether or
One or more mixtures of gasoline；Second tension controller is set after coating slot, the film wire after coating enters the second baking oven, the
The temperature of two baking ovens is controlled at 40 DEG C -100 DEG C, and the solvent of coating solution is made to volatilize, and coating material is still retained in " lacking for film wire
Fall into " at, film wire surface is repaired；Film wire after repairing carries out solidification case, and the temperature of solidification case is controlled at 70 DEG C -250 DEG C,
Oxygen content is lower than 1% in solidification case；Film wire, by third tension controller, controls film wire gathering speed after solidification case, complete
At the preparation of hollow-fibre membrane.
Based on above technical scheme, it is preferred that if the first outer coagulation bath and the second outer coagulation bath use methanol, ethyl alcohol,
One of isopropanol or a variety of mixtures do not need setting displacement bath then.
Based on above technical scheme, it is preferred that tension is arranged according to the contraction situation of film wire in the film wire preparation process
Control point.The effect of tension controller is to control the hauling speed of film wire in subsequent process.Usually in the first outer coagulation bath, second
Driving wheel is configured in outer coagulation bath and displacement slot, the first tension controller is arranged after displacement slot, and tension force is at 0.5 N
Pause -5 newton, and the second tension controller is arranged after coating slot, and tension force is in -5 newton of 0.5 newton, third tension controller
It is arranged after solidification case, for controlling the speed of wire drawing wheel.Tension force is in -5 newton of 0.5 newton.First outer gel slot, the
Hauling speed in two outer gel slots and displacement slot is greater than coating process speed, and coating process speed is slightly larger than curing process speed
With collection wheel speed.Wire drawing wheel speed control is at 5 ms/min -60 ms/min.
Further aspect of the present invention provides a kind of Ho llow fiber membrane for gas separation that above-mentioned preparation method is prepared, film wire
At 200 μm -800 μm, internal diameter is controlled at 100 μm -600 μm for outer diameter control.
The present invention also provides a kind of applications of above-mentioned Ho llow fiber membrane for gas separation, and the hollow fiber film thread of the preparation can
To be prepared into the membrane module of different size, the gas for different field is separated, such as oxygen and nitrogen separation, helium, hydrogen and
The separation etc. of nitrogen separation, hydrogen and carbon dioxide separation, carbon dioxide and methane separation, xenon and oxygen separation.
Beneficial effect
(1) present invention provides a kind of integration system for the device of Ho llow fiber membrane for gas separation, effectively by the spinning of film wire
Silk technique, drying process, coating process and curing process connect, and reduce film wire manufacturing cycle, while reducing manual operation
Link improves film wire stability.
(2) difficult point of integrated film wire preparation process is by the spinning technique of film wire, drying process, coating process and solidification
Technique connects, and technical process is very long, and film wire is very thin, therefore in integrated film wire preparation process, film wire tension force is very
It is important.Spinning technique, coating process, curing process and the film wire collection process of film wire of the present invention are carried out by tension controller
Connection effectively controls the film wire speed in different process stage, effectively avoids film wire in integrated preparation process by tension force
In be stretched deformation and the case where break, tension force of the present invention is mainly from the aspect of two: first, tension is in certain range
It is interior.Tension is big, and film wire is easy to be pulled off, and tension is small, and film wire can not be drawn；Second, it, must in hollow fiber film thread preparation process
It must consider the shrinking percentage of film wire, the contraction of film wire is while the and film as caused by the abjection of moisture in film wire under normal conditions
Material is related to process conditions.According to analysis above, usual tension setpoints after coating slot and solidify after displacement slot
After shaping box, tension force is in -5 newton of 0.5 newton.With the reduction of the water content of film wire, the shrinkage of film wire gradually subtracts
It is small.
(3) hauling speed of the film wire of the present invention in the first outer gel slot, the second outer gel slot and displacement slot is greater than coating
Process speed, coating process speed is slightly larger than curing process speed and collects wheel speed.Tension force effect is to control not same order
The spinning speed of section.By tension force, the film wire speed in different process stage is effectively controlled, effectively avoids film wire in integration
Be stretched the case where deforming and breaking in preparation process.
(4) preparation facilities of the invention and technique improve the uniformity of film wire coating.In the technique of segmentation preparation film wire,
Hundreds of thousands root film wire set bunchy is arrived by tens of thousands of in the coating procedure of film wire, is placed into coated pipe and stands or vacuumize progress
Coating, the phenomenon that this method be easy to cause coating solution uneven in the coating of film wire surface.Film wire integral preparation method is effectively kept away
Exempt from such case, by coated pipe in a manner of single film wire, improves the uniformity of film wire coating.
(5) preparation facilities of the invention and technique improve the uniformity of film wire solidification process.It is identical as coating procedure, dividing
In the technique of section preparation film wire, the solidification of film wire arrives hundreds of thousands root film wire set bunchy for tens of thousands of, be placed into solidification case into
Row high-temperature process, the heated situation of film wire has differences inside the heated situation and film wire beam of the film wire outside film wire beam.Film wire
Integral preparation method effectively avoids such case, by solidification case in a manner of single film wire, improves film wire solidification process
Uniformity.
Detailed description of the invention
Fig. 1 is the preparation facilities schematic diagram of one-step method hollow-fibre membrane of the present invention；Wherein: 101 material-compound tanks；102 Debubbling tanks；
103 inner gel tanks；104 gear pumps；105 metering pumps；106 porous spray plates；107 first outer gel slots；108 second outer gel slots；
109 displacement slots；110 first tension controllers；111 first baking ovens；112 coating slots；113 second tension controllers；114 second dry
Case；115 solidification cases；116 third tension controllers；117 film wire wire drawing wheels.
Fig. 2 is segmented doughnut membrane preparation device and technique；Wherein: 201 material-compound tanks；202 Debubbling tanks；It is coagulated in 203
Glue tank；204 gear pumps；205 metering pumps；206 porous spray plates；207 the first outer gel slots with driving wheel；208 with driving wheel
Second outer gel slot；209 displacement slots with driving wheel；210 tension controllers；211 wire drawing wheels.
Fig. 3 is the plater and technique of segmented hollow-fibre membrane；Wherein: 301 insulating layers；302 coated pipes；In 303
Empty fiber membrane core；304 coating solution feed inlets；305 coating solution drain holes.
Fig. 4 is the solidification equipment and technique of segmented hollow fiber film thread；Wherein: 401 solidification cases；402 film cores.
Specific embodiment
The present invention is described in further details combined with specific embodiments below, but is not limited to specific embodiment.
Solvent with water content is analyzed using gas-chromatography in film wire.
Properties of sample (including non-coated film silk and coating film wire) test method of hollow fiber film thread is as follows:
(1) preparation of sample
Take it is dry after certain length, a certain number of hollow-fibre membranes, be converted into U-shaped, open end is cast into epoxy resin
Test sample forms hollow-fibre membrane test sample.
(2) test method:
1, the temperature control system of opening test device, setting test temperature, usually 30 DEG C.
2, test sample is put into test device.Test gas piping is connected with nitrogen (purity >=99%) gas source, beats
Open Nitrogen source gases, displacement test pipeline five times；Gas test pressure is adjusted, 0.5MPa is typically set at, after stablizing 15 minutes, benefit
Pass through the gas flow Q of film wire with testing flow meter nitrogenN2, in triplicate, it is averaged, is completed, closes Nitrogen source gases.
3, test gas piping is connected with oxygen (purity >=99%) gas source, opens oxygen source, displacement test pipeline
Five times；Gas test pressure is adjusted, 0.5MPa is typically set at, after stablizing 15 minutes, passes through film using testing flow meter oxygen
The gas flow Q of silkO2, in triplicate, it is averaged, is completed, closes oxygen source.
The calculating of infiltration rate:
Ji=Qi/(AΔP)
Wherein JiPass through the infiltration rate of hollow-fibre membrane, (1GPU=1 × 10 GPU for gas i-6cm3(STP)/cm2·
s·cmHg)；QiFor the volume flow of gas i at standard temperature and pressure, cm3(STP)/s；A is overall effective membrane area,
cm2；Δ P is the pressure difference of film two sides, cmHg.
The calculating of separation:
The pure gas i of two kinds of differences, the permselective property of j are generally used gas selectivity α i/j to express, are calculate by the following formula:
αij=Ji/Jj
As described in Figure 1, the preparation facilities of hollow-fibre membrane of the invention includes: material-compound tank 101；Debubbling tank 102；Inner gel
Tank 103；Gear pump 104；Metering pump 105；Porous spray plate 106；First outer gel slot 107；Second outer gel slot 108；Displacement slot
109；First tension controller 110；First baking oven 111；Coating slot 112；Second tension controller 113；Second baking oven 114；Gu
Change case 115；Third tension controller 116；Film wire wire drawing wheel 117；The first outer gel slot 107；Second outer 108 He of gel slot
Displacement slot 109 is equipped with driving wheel, the traction for film wire；It is equipped in first baking oven, coated pipe, the second baking oven and solidification case
Control of the speed of guide wheel, first baking oven and coated pipe guide wheel by the first tension controller, second baking oven and solidification
The speed of case guide wheel is controlled by the second tension controller, and the film wire collects wheel speed by the control of third tension controller；
Raw material is added in material-compound tank 101 and mixes, and after 102 deaeration of Debubbling tank, is delivered to porous spray by gear pump 104
Plate, inner gel tank 103 are provided with inner gel liquid, and inner gel liquid enters first after being conveyed through porous spray plate 106 by metering pump 105
Outer gel slot 107 forms film wire, is next successively drawn past the second outer gel slot 108, displacement slot by driving wheel, guide wheel
109；First baking oven 111, coating slot 112, the second baking oven 114, solidification case 115, are finally collected by film wire wire drawing wheel 117.
Embodiment 1
By 340 grams of polysulfones, 640 grams of dimethyl acetamide, 20 grams of calcium nitrate are added in material-compound tank, under the conditions of 80 DEG C
Stirring 60 hours enters Debubbling tank until polysulfones is completely dissolved under pressure, by vacuum defoamations in 84 hours and ripe
Change, forms film liquid.Film liquid and inner gel liquid carry out coagulation bath, the first outer gel into the first outer gel slot by porous spray plate
Bath is water, and film wire is 5 seconds in the residence time of the first outer gel slot, and at 50 ms/min, phase occurs driving wheel speed control for film liquid
Transformation forms nascent state hollow fiber film thread；Film wire enters the second outer coagulation bath, and the second outer coagulation bath is water, will be in film wire
For exchange of solvent into water, film wire is 30 seconds in the residence time of the second outer gel slot, driving wheel speed control at 53 ms/min,
The content of solvent A is lower than 1.0% in film wire；Film wire enters displacement bath, selects isobutanol as displacement liquid, film wire is in displacement bath
Residence time be 30 seconds, the moisture content 1.8% in film wire；Before film wire enters the first baking oven, a tension force point is set,
Tension force controls film wire and enters the first baking oven and coat speeds, speed is 51 ms/min in 2.5 ± 0.5 newton；Film wire into
Enter the first baking oven, the temperature of the first baking oven is controlled at 100 DEG C；Film wire enters coated pipe and carries out surface reconditioning, and temperature is controlled 10
DEG C, the coating solution in coated pipe is 5% silicone rubber solution, and solvent is pentane；One tension force is set after film wire coating
Point, tension force control the speed that film wire enters the second baking oven and solidification case in 2.0 ± 0.5 newton, and speed is 49 ms/min
Film wire after reparation enters the second baking oven, and the temperature of the second baking oven is controlled at 60 DEG C, so that the solvent of coating solution is volatilized, coating material
It is still retained at " defect " of film wire, film wire surface is repaired；Film wire after repairing carries out solidification case, the temperature of solidification case
Degree control is at 200 DEG C, oxygen content 0.8% in solidification case；A tension force point is arranged in film wire before collection, and tension force exists
1.5 ± 0.5 newton.Film wire after solidification is collected using wire drawing wheel, and wire drawing wheel speed is 47 ms/min.
Comparative example 1
Hollow-fibre membrane is prepared using discrete method, specific process flow is as follows:
By 340 grams of polysulfones, 640 grams of dimethyl acetamide, 20 grams of calcium nitrate are added in material-compound tank, are stirred in 80 DEG C of conditions
It mixes 60 hours, forms uniform Polymer Solution.Solution passes through vacuum defoamation and curing in 96 hours, forms film liquid.Film liquid and
Inner gel liquid is by porous spray plate, and into the first outer gel slot, the coagulation bath in the first outer gel slot is water, and film wire is outside first
The residence time of gel slot is 5 seconds, and phase transition occurs for film liquid, forms nascent state hollow fiber film thread, collects film wire using film wire
Wheel is collected into, wire drawing wheel speed is 50 ms/min.
After film wire is collected into wheel, impregnates in the sink, be used for exchange of solvent 5 days~10 days, film wire is then put into baking oven
In, sizing is dried, temperature is controlled at 100 DEG C.
The coating of film wire.There is a small amount of " defect " in the surface using the hollow fiber film thread of phase transition method preparation, will be several
Ten thousand are arrived hundreds of thousands root film wire set bunchy, are placed into coated pipe and are stood or vacuumize carry out coating, need to apply using surface
The technology of applying, repairs " defect " on film wire surface.Film core enters coated pipe and carries out surface reconditioning, and temperature is controlled at 10 DEG C,
Coating solution in coated pipe is 5% silicone rubber solution, and solvent is pentane.
The solidification of coating material.Tens of thousands of after coating are placed in baking oven to hundreds of thousands root film wire set bunchy and are consolidated
Change, the control of the temperature of solidification case is at 200 DEG C, oxygen content 0.8% in solidification case.
Embodiment 2
400 grams of polyetherimide is dissolved in the mixing of 420 grams of N- methyl arsenic pyrrolidone and 180 grams of gamma-butyrolactons
It in solvent, is stirred 60 hours under the conditions of 80 DEG C, until polyetherimide is completely dissolved, into Debubbling tank, by 96 hours
Vacuum defoamation and curing form film liquid.Film liquid and inner gel liquid are solidifying outside first into the first outer gel slot by porous spray plate
The coagulation bath of glue groove is water, and film wire is 30 seconds in the residence time of the first outer coagulation bath, and phase transition occurs for film liquid, forms nascent state
Hollow fiber film thread, driving wheel speed control is at 10 ms/min；Film wire enters the second outer gel slot, and the second outer coagulation bath is usual
Water is selected, by the exchange of solvent in film wire into water, film wire is 300 seconds in the residence time of the second outer coagulation bath, active wheel speed
Control is at 12 ms/min, the content 0.5% of solvent in film wire；Film wire enters displacement slot, selects isobutanol as displacement liquid, film
Residence time of the silk in displacement slot is 240 seconds, guarantees the moisture content 1.0% in film wire；Before film wire enters the first baking oven, if
A tension force point is set, tension force is in 2.0 ± 0.5 newton, and speed control is at 11 ms/min；Film wire enters the first baking oven,
The temperature of first baking oven is controlled at 150 DEG C；Film wire enters coating slot and carries out surface reconditioning, and temperature controls in 20 DEG C, coating slot
Coating solution be 1.5% silicone rubber solution, solvent is pentane；One tension force point, tension control are set after film wire coating
System is in 1.5 ± 0.5 newton, and for speed control at 10 ms/min, the film wire after reparation enters the second baking oven, the temperature of the second baking oven
At 60 DEG C, film wire after repairing carries out solidification case for control, and the temperature control of solidification case is at 250 DEG C, oxygen content in solidification case
0.8%；A tension force point is arranged in film wire before collection, and in 1.0 ± 0.5 newton, the film wire after solidification utilizes tension force
Wire drawing wheel is collected, and speed control is at 9 ms/min.
Comparative example 2
400 grams of polyetherimide is dissolved in 420 grams of N- methyl arsenic pyrrolidone and mixed with 180 grams of gamma-butyrolactons
It in solvent, is stirred 60 hours under the conditions of 80 DEG C, until polyetherimide is completely dissolved, into Debubbling tank, by 96 hours
Vacuum defoamation and curing, formed film liquid.Film liquid and inner gel liquid are by porous spray plate, into the first gel slot, the first gel
Coagulation bath in slot is water, and film wire is 20 seconds in the residence time of the first outer coagulation bath, and phase transition occurs for film liquid, forms nascent state
Hollow fiber film thread, driving wheel speed control is at 40 ms/min；Film wire enters the second outer coagulation bath, in the second outer gel slot
Coagulation bath is water, and by the exchange of solvent in film wire into water, film wire is 200 seconds in the residence time of the second outer gel slot, actively
Wheel speed is controlled at 43 ms/min, the content 1.0% of solvent in film wire；Film wire enters displacement slot, selects isobutanol as displacement
Liquid, residence time of the film wire in displacement bath is 180 seconds, guarantees the moisture content 1.5% in film wire；Film wire enters the first baking oven
Before, a tension force point is set, and tension force is in 2.0 ± 0.5 newton；Film wire enter the first baking oven, speed control 41 meters/
Minute, the temperature of the first baking oven is controlled at 100 DEG C；Film wire enters coated pipe and carries out surface reconditioning, and temperature control is at 10 DEG C, coating
Coating solution in pipe is 1% silicone rubber solution, and solvent is pentane；One tension force point, tension are set after film wire coating
Control is in 3.0 ± 0.5 newton, and for speed control at 40 ms/min, the film wire after reparation enters the second baking oven, the temperature of the second baking oven
At 60 DEG C, film wire after repairing carries out solidification case for degree control, and the temperature control of solidification case is at 200 DEG C, oxygen content in solidification case
Lower than 1%；A tension force point is arranged in film wire before collection, film wire benefit of the tension force in 6.0 ± 0.5 newton, after solidification
It is collected with wire drawing wheel, speed control is at 46 ms/min.
Embodiment 3
By 250 grams of polyimides, 600 grams of N- methyl arsenic pyrrolidone, 130 grams of gamma-butyrolactons, 20 grams of lithium nitrates additions
It in material-compound tank, is stirred 60 hours under the conditions of 80 DEG C, until being completely dissolved, into Debubbling tank, by vacuum defoamation in 96 hours
And curing, form film liquid.Film liquid and inner gel liquid are by porous spray plate, into the first outer gel slot, in the first outer gel slot
Coagulation bath is methanol, and film wire is 15 seconds in the residence time of the first outer gel slot, and phase transition occurs for film liquid, and it is hollow to form nascent state
Fiber film wire, driving wheel speed control is at 35 ms/min；Film wire enters the second outer gel slot, the gel in the second outer gel slot
Bath is methanol, and film wire is 130 seconds in the residence time of the second outer gel slot, and driving wheel speed control is at 38 ms/min, in film wire
The content of solvent is lower than 1%；Before film wire enters the first baking oven, a tension force point is set, and tension force is at 2.0 ± 0.5 Ns
, speed control is at 36 ms/min；Film wire enters the first baking oven, and the temperature of the first baking oven is controlled at 90 DEG C；Film wire enters coating
Slot carries out surface reconditioning, and coating solution of the temperature control in 25 DEG C, coating slot is 0.5% silicone rubber solution, and solvent is positive penta
Alkane；One tension force point is set before film wire coating, and tension force is repaired in 1.5 ± 0.5 newton, speed control at 34 ms/min
Film wire after multiple enters the second baking oven, and the temperature of the second baking oven controls the film wire at 60 DEG C, after repairing and carries out solidification case, solidification case
Temperature control at 200 DEG C, oxygen content 0.5% in solidification case；A tension force point, tension control is arranged in film wire before collection
System is in 1.0 ± 0.5 newton, and the film wire after solidification is collected using wire drawing wheel, and speed control is at 33 ms/min.
Table 1
Table 1 is the manufacturing cycle and film wire performance of different film wire preparation methods, the different membrane materials known to embodiment 1,2,3
The hollow fiber film thread performance of preparation is different.Embodiment 1 and comparative example 1 use in comparative example 1 using polysulfones as membrane material
Segmented preparation process, the formation of nascent state film wire, sizing, coating, solidification and film wire collect each preparation process independence, lead to film wire
Manufacturing cycle is -20 days 15 days, and the connection of each preparatory phase needs to complete by manual process, manual process not really
It is qualitative to will lead to film wire performance unstability；Simultaneously because using segmented preparation method in the comparative example, coating procedure will be several
Ten thousand are bundled together to form film core with hundreds of thousands root film wire collection, are placed on coated pipe and carry out coating, the stability of coating procedure is not so good as
It is uniform in integrated film wire preparation method, similarly in solidification process, the film core of tens of thousands of and hundreds of thousands root film wire are put into baking oven
In solidified, the heated situation of the heated situation of the film wire on the outside of film core and the film wire in film core inner is different, can
It is unstable solidification process to be will lead to.And integral preparation process is utilized in embodiment 1, the preparation process prosthetic of entire film wire
Operation, the preparation time of film wire 30 minutes, production efficiency significantly improves, and film wire coating procedure and solidification process uniformity
Good, film wire performance is apparently higher than comparative example 1 in embodiment 1.
In comparative example 2 and embodiment 2, being all made of polyetherimide is membrane material, third tension force in comparative example 2
Value is 6.0 ± 0.5 newton, goes beyond the scope, film wire is caused to stretch during collection, and film wire surface is caused more " lack occur
Fall into ", influence film wire performance.With should the tension value of the first tension force point and the second tension force go beyond the scope, equally can be right
Film wire generates stretching, influences film wire performance.In embodiment 2 in film wire preparation process tension force within the scope of, therefore prepare
Film wire better performances out.
In embodiment 2 and implement to use polyimide engineering plastics for membrane material in 3, prepares hollow fibre using one-step method
Film wire is tieed up, not only membrane preparation cycle is most short, but also film wire performance is relatively good, and the hollow fiber film thread of preparation can be prepared into different rule
The membrane module of lattice, the gas for different field separates, such as oxygen and nitrogen separation, helium, hydrogen and nitrogen separation, xenon with
The separation etc. of oxygen separation.
Claims (10)
1. a kind of Ho llow fiber membrane for gas separation preparation facilities, which is characterized in that described device successively includes porous spray plate, first
Outer gel slot, the second outer gel slot, displacement slot, the first tension controller, the first baking oven, coating slot, the second tension controller,
Two baking ovens, solidification case, third tension controller and film wire collecting wheel；The first outer gel slot, the second outer gel slot and displacement
Slot is provided with driving wheel, and the driving wheel is used to draw the film formed in the first outer gel slot, the second outer gel slot and displacement slot
Silk, is equipped with guide wheel in first baking oven, coated pipe, the second baking oven and solidification case, first baking oven and coated pipe guide wheel
Speed is by the control of the first tension controller, and the speed of second baking oven and solidification case guide wheel is by the second tension controller control
System, the film wire collect wheel speed by the control of third tension controller.
2. Ho llow fiber membrane for gas separation preparation facilities according to claim 1, which is characterized in that described device further includes
Material-compound tank, Debubbling tank, inner gel tank, gear pump and metering pump, the solution of the material-compound tank are defeated by gear pump after Debubbling tank
It send to porous spray plate；The solution of the inner gel tank is delivered to porous spray plate by metering pump.
3. a kind of Ho llow fiber membrane for gas separation preparation method, which is characterized in that use device as claimed in claim 2, include
Following steps:
(1) by high molecular material, solvent A is added in material-compound tank, stirred 48 hours in 50~100 DEG C of conditions or more, it is formed high
Molecular solution；
(2) Polymer Solution enters Debubbling tank, by vacuum defoamation and curing in 72-120 hours, forms film liquid；
(3) film liquid and inner gel liquid are thrown into porous spray plate respectively using gear pump and metering pump, into the first outer gel slot into
Phase transition process occurs for row gel, forms nascent state hollow fiber film thread；Nascent state hollow fiber film thread enters solidifying outside second
Glue groove carries out gel, and exchange of solvent occurs, and solvent remaining in film wire is all discharged, the solvent A content in film wire is lower than
1%；
(4) sizing is dried into the first baking oven in the film wire of step (3), and the temperature of baking oven is controlled at 90 DEG C~150 DEG C；
(5) film wire of step (4), which enters, carries out coating in coating slot, coating slot has collet, and the temperature of coating slot is controlled at 5 DEG C
~30 DEG C；
(6) film wire of step (5) enters the second baking oven, and the second oven temperature is controlled at 40 DEG C~100 DEG C；
(7) film wire of step (6) enters solidification case, and the temperature control of the solidification case is at 70 DEG C~250 DEG C, oxygen in solidification case
Content is lower than 1%；
(8) it is collected using wire drawing wheel, ultimately forms the hollow fiber film thread.
4. Ho llow fiber membrane for gas separation preparation method according to claim 3, which is characterized in that the first tension control
The tension of device processed is -5 newton of 0.5 newton；The tension of second tension controller is -5 newton of 0.5 newton, the third
The tension force of force controller is -5 newton of 0.5 newton；Film in the first outer gel slot, the second outer gel slot and displacement slot
Silk hauling speed is greater than the coating process speed in coating slot, and the coating process speed is greater than solidification in-tank-solidification process speed
Wheel speed is collected with film wire；The wire drawing wheel degree control is at 5 ms/min -60 ms/min.
5. Ho llow fiber membrane for gas separation preparation method according to claim 3, it is characterised in that: step (1) described height
It further include inorganic salts in molecular solution；The high molecular material is polyimides, polyetherimide, polysulfones, polyether sulfone, polypropylene
It is at least one of fine；The solvent A is that N- methyl pyrrole irons alkanone, n,N-Dimethylformamide, n,N-dimethylacetamide, two
Methyl sulfoxide, sulfolane, gamma-butyrolacton, at least one of N- methyl piperidine；The inorganic salts are lithium chloride, potassium chloride, nitre
Sour potassium, at least one of lithium nitrate；The mass ratio of the high molecular material, solvent A and inorganic salts are as follows: 25-40:35-75:
0.01-5。
6. Ho llow fiber membrane for gas separation preparation method according to claim 3, it is characterised in that: in the first outer gel slot
Coagulation bath and the second gel slot in coagulation bath be independently selected from non-solvent, the non-solvent is water, methanol, ethyl alcohol, propyl alcohol,
At least one of isopropanol；Film wire the first outer gel slot residence time in 5-30s；Stop of the film wire in the second gel slot
Time is 30-300s.
7. Ho llow fiber membrane for gas separation preparation method according to claim 6, it is characterised in that: when the first outer coagulation bath
When using water simultaneously with the second outer coagulation bath, film wire is after the second outer gel slot, and into displacement slot, the solution in displacement slot is
One of ethyl alcohol, propyl alcohol, isopropanol；Film wire residence time in displacement slot is 30-240s, and film wire is after displacement slot, film
Moisture content is lower than 2% in silk.
8. Ho llow fiber membrane for gas separation preparation method according to claim 3, it is characterised in that: in the coating slot
The silicone rubber solution that liquid is 0.1%~10%, the solvent of the silicone rubber solution are pentane, normal hexane, petroleum ether, gasoline
One or more mixtures.
9. the hollow fibre that Ho llow fiber membrane for gas separation preparation method described in a kind of claim 3-8 any one is prepared
Tie up gas separation membrane, which is characterized in that the outer diameter of the Ho llow fiber membrane for gas separation is 200-800 μm, internal diameter 100-600
μm。
10. a kind of application of Ho llow fiber membrane for gas separation as claimed in claim 9, which is characterized in that the doughnut gas
Body seperation film is used for oxygen and nitrogen separation, hydrogen and nitrogen separation, helium and nitrogen separation, hydrogen and carbon dioxide separation,
The separation of carbon dioxide and methane separation and xenon and air.
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| US20160367935A1 (en) * | 2016-08-31 | 2016-12-22 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Defect-free carbon molecular sieve membranes with enhanced selectivity and aging resistance and the method of making the same |
| CN109289553A (en) * | 2018-10-26 | 2019-02-01 | 德蓝水技术股份有限公司 | Continuously prepare the device and method of hollow fiber composite membrane |
| CN110075719A (en) * | 2019-05-30 | 2019-08-02 | 北京化工大学 | The preparation method of high-throughput polyacrylonitrile hollow fiber composite gas separation membrane |
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| CN101658763A (en) * | 2009-09-14 | 2010-03-03 | 天津工业大学 | Equipment based on LabView control for coating hollow fiber membrane |
| CN103492056A (en) * | 2011-04-20 | 2014-01-01 | 三菱丽阳株式会社 | Porous film production method and device |
| US20160367935A1 (en) * | 2016-08-31 | 2016-12-22 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Defect-free carbon molecular sieve membranes with enhanced selectivity and aging resistance and the method of making the same |
| CN109289553A (en) * | 2018-10-26 | 2019-02-01 | 德蓝水技术股份有限公司 | Continuously prepare the device and method of hollow fiber composite membrane |
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