CN107106995A - 碳膜用制膜原液及使用其的碳中空纤维膜的制备方法 - Google Patents
碳膜用制膜原液及使用其的碳中空纤维膜的制备方法 Download PDFInfo
- Publication number
- CN107106995A CN107106995A CN201580059047.8A CN201580059047A CN107106995A CN 107106995 A CN107106995 A CN 107106995A CN 201580059047 A CN201580059047 A CN 201580059047A CN 107106995 A CN107106995 A CN 107106995A
- Authority
- CN
- China
- Prior art keywords
- film
- carbon film
- hollow
- stoste
- wet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000000835 fiber Substances 0.000 title description 44
- 239000012528 membrane Substances 0.000 title description 44
- 229920006380 polyphenylene oxide Polymers 0.000 claims abstract description 31
- 235000012489 doughnuts Nutrition 0.000 claims abstract description 30
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 28
- 239000012298 atmosphere Substances 0.000 claims abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005864 Sulphur Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000003763 carbonization Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000011550 stock solution Substances 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 37
- 239000000126 substance Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 239000007792 gaseous phase Substances 0.000 claims 1
- 150000001451 organic peroxides Chemical class 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 11
- 238000009987 spinning Methods 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012545 processing Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000001112 coagulating effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 239000012510 hollow fiber Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229940113088 dimethylacetamide Drugs 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- -1 -3- hexins Chemical class 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 210000004907 gland Anatomy 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NOSXUFXBUISMPR-UHFFFAOYSA-N 1-tert-butylperoxyhexane Chemical compound CCCCCCOOC(C)(C)C NOSXUFXBUISMPR-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N acetaldehyde dimethyl acetal Natural products COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Classifications
-
- 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
- B01D69/087—Details relating to the spinning process
-
- 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
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0067—Inorganic membrane manufacture by carbonisation or pyrolysis
-
- 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
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0072—Inorganic membrane manufacture by deposition from the gaseous phase, e.g. sputtering, CVD, PVD
-
- 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
-
- 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
- B01D69/087—Details relating to the spinning process
- B01D69/0871—Fibre guidance after spinning through the manufacturing apparatus
-
- 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
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/04—Dry spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- B01D2053/221—Devices
- B01D2053/223—Devices with hollow tubes
- B01D2053/224—Devices with hollow tubes with hollow fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/08—Specific temperatures applied
- B01D2323/081—Heating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/218—Additive materials
- B01D2323/2181—Inorganic additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/218—Additive materials
- B01D2323/2182—Organic additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/0283—Pore size
- B01D2325/02831—Pore size less than 1 nm
-
- 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
- Y02C20/20—Capture or disposal of greenhouse gases of methane
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Mechanical Engineering (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Inorganic Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
碳膜用制膜原液,在制膜原液中,达到15~40重量%的浓度的量的聚苯醚和在该聚苯醚和硫的总重量中达到0.1~5.0重量%、优选0.2~3.0重量%的比例的量的硫溶解在可溶解它们的溶剂中。使用双重环状喷嘴,通过湿式或干湿式纺丝法将该碳膜用制膜原液成型为中空状,在空气中于150~350℃加热从而不熔化处理后,在惰性气氛或真空中于600~800℃加热来进行碳化处理,由此制备中空纤维碳膜。若将通过湿式或干湿式纺丝法成型为中空状的产品一边于0.002~0.005MPa的应力下拉伸,一边在空气中加热从而不熔化处理,则得到气体透过性优异且分离系数(He/CH4)更为优异的中空纤维碳膜。
Description
技术领域
本发明涉及碳膜用制膜原液及使用其的碳中空纤维膜的制备方法。更详细而言,涉及将聚苯醚作为主要成分的碳膜用制膜原液及使用其的、气体分离性能优异的碳中空纤维膜的制备方法。
背景技术
一直以来,作为分离膜提出了各种的有机膜、无机膜。但是,虽然有机膜廉价且成型性优异,但耐溶剂性、耐热性低,另一方面陶瓷膜等无机膜与有机膜相反,耐溶剂性、耐热性优异,但发现有高价且成型困难这样的问题。
因此,近年来,虽然是无机膜,但成型性优异且廉价的碳膜受到关注。由于中空纤维碳膜具有可分离气体的尺寸的孔,在各种的无机膜中显示优异的气体分离性能,并且在要求对无法应用有机膜的约70~150℃这样的高温度的耐热性和耐化学药品性、耐溶剂性的环境下也可使用,所以其实用性备受期待。另外,中空纤维膜具有耐压性优异,并且每单位容积所占的膜面积大,可制备紧密的分离膜模件这样的优点。
到目前为止,作为中空纤维碳膜,提出了作为原料例如使用将聚苯醚磺化而得的树脂的中空纤维碳膜(专利文献1~2)、使用芳族聚酰亚胺的中空纤维碳膜(专利文献3)。
然而,磺化聚苯醚由于其本身并非通用性材料,所以需要将聚苯醚磺化的合成工序,另一方面芳族聚酰亚胺的合成需要在有机溶剂中的反应,但由于难以确保在该有机溶剂中的溶解性,所以会成为特殊的制备方法。如上所述,将磺化聚苯醚或芳族聚酰亚胺作为原料的碳膜由于原料高价,或其原料制备、制膜工序复杂,所以有膜成本会升高这样的问题。
另一方面,还提出了作为原料使用廉价的聚苯醚的中空纤维碳膜(专利文献4)。但是,由于只有聚苯醚则分离性低,所以为了确保分离性,需要在聚苯醚膜上层合磺化聚苯醚树脂后,进行煅烧处理这样的复杂构成,制备工序会变得繁杂,因此有即使使用廉价的原料,反而成本升高这样的缺点。
通常,在碳膜使用任意原料的情况下,都需要实施以下2个阶段的加热,即在将中空纤维纺丝并切割为规定的长度后,实施插入PFA树脂制等的管中并在空气中于约250~350℃加热的“不熔化处理”,然后实施在惰性气氛或真空中于约600~800℃进行加热的“碳化处理”。
因此,为了制备性价比优异的碳膜中空纤维膜,要求使用廉价的材料将中空纤维纺丝,并且不采用繁杂的工序,而将不熔化处理工序和碳化处理工序这2个阶段的加热工序作为主要工序的制备方法。
此外,对氦、氢、水蒸气等的透过速度快,这些气体的分离性高,并且高功能的碳膜的迫切要求也高涨。
现有技术文献
专利文献
专利文献1:日本特开2009-34614号公报
专利文献2:日本特开2013-94744号公报
专利文献3:日本特开2000-185212号公报
专利文献4:日本特开2013-63415号公报
专利文献5:日本特开昭62-30508号公报
专利文献6:日本特开昭63-28406号公报
专利文献7:日本特开平7-51551号公报。
发明内容
发明所要解决的课题
本发明的目的在于,提供将聚苯醚作为主要成分,使用通用性材料,可制备高气体分离性能等高功能的碳膜的碳膜用制膜原液及使用其的中空纤维碳膜的制备方法。
解决课题的手段
上述本发明的目的可通过如下的碳膜用制膜原液达成,在制膜原液中,达到15~40重量%的浓度的量的聚苯醚和在该聚苯醚和硫的总重量中达到0.1~5.0重量%、优选0.2~3.0重量%的比例的量的硫溶解在可溶解它们的溶剂中;使用双重环状喷嘴,通过湿式或干湿式纺丝法将该碳膜用制膜原液成型为中空状,在空气中于150~350℃加热从而不熔化处理后,在惰性气氛或真空中于600~800℃加热来进行碳化处理,由此制备中空纤维碳膜。优选将通过湿式或干湿式纺丝法成型为中空状的产品一边于0.002~0.005MPa的应力下拉伸,一边在空气中加热从而不熔化处理。
发明的效果
由于本发明所涉及的制膜原液中使用的材料均为通用性材料,纺丝方法也可应用与通常的工业用水处理膜相同的方法,所以起到使得中空纤维碳膜制备的低成本化和量产性的提高成为可能,同时可制备高气体分离性能等高功能的碳膜等的优异效果。
另外,作为气体分离用的膜,为了调整与使用条件对应的膜强度、透过速度,希望可以任意尺寸调整中空纤维的内外径和膜厚;通过使用本发明所涉及的制备方法,可将纺丝阶段的中空纤维在外径为500~3000μm、并且壁厚为50~1000μm的范围内任意地调整,在膜设计方面可灵活的应对。
此外,由于制膜而得的碳膜具有高分离性能,所以也起到能够提高透过侧的低分子气体的纯度这样的效果。特别是在一边施加应力一边拉伸的同时,在空气中加热从而不熔化处理过的产品,在得到的碳中空纤维膜中形成直径为1nm以下的多孔性孔,因此可得到气体透过性优异且气体分离系数高的中空纤维碳膜。
附图说明
图1是表示在实施例1中纺丝、干燥后得到的中空纤维膜的SEM放大照片(×55)的图。
图2是表示在实施例1中纺丝、干燥后得到的中空纤维膜的SEM放大照片(×100)的图。
图3是表示在实施例1中不熔化、碳化处理干燥后得到的中空纤维碳膜的SEM放大照片(×170)的图。
图4是表示在比较例1中纺丝、干燥后得到的中空纤维膜的SEM放大照片(×55)的图。
图5是表示在比较例1中纺丝、干燥后得到的中空纤维膜的SEM放大照片(×100)的图。
图6是表示在比较例1中不熔化、碳化处理干燥后得到的中空纤维碳膜的SEM放大照片(×130)的图。
图7是在气体分子直径与气体透过速度的关系方面将在实施例1~2和比较例1~2中进行的气体透过试验的结果作曲线而得的曲线图。
具体实施方式
作为聚苯醚,可直接使用市售品,例如SABIC公司制品PPO646,MitsubishiEngineering-Plastics Corporation制品PX100F、PX100L等,将其在制膜原液中以约15~40重量%、优选约20~35重量%的比例使用。在聚苯醚的浓度比该浓度高的情况下,制膜原液会分离而无法纺丝,另一方面在比该浓度低的情况下,在煅烧时变脆而有无法得到良好的碳膜的情况。
在制膜原液中,进一步添加在聚苯醚和硫的总重量中达到0.1~5.0重量%、优选0.2~3.0重量%的比例的量的硫。在硫的比例比该比例多的情况下,制膜原液会分离而无法纺丝,另一方面在比该比例少的情况下,无法看到通过添加硫得到的高气体分离性能等效果。
在制膜原液中,也可与硫一起添加使用具有交联效果的二(2-叔丁基过氧异丙基)苯、二枯基过氧化物、2,5-二甲基-2,5-二(叔丁基过氧)己烷、2,5-二甲基-2,5-二(叔丁基过氧)-3-己炔等二烷基系过氧化物,二异丁酰基过氧化物等二酰基系过氧化物等有机过氧化物;酚醛树脂交联剂;醌二肟交联剂等。
碳膜用制膜原液的制备是通过将聚苯醚、硫(和添加剂)溶解在可溶解它们的溶剂中来进行。溶解是通过首先将硫溶解在溶剂中后,溶解聚苯醚来进行。作为上述溶剂,可列举出甲醇、乙醇、四氢呋喃、N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮等,优选使用N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮等非质子性极性溶剂。
在这里,若在纺丝时纺丝原液会相分离,则无法进行稳定的纺丝,因此纺丝、制膜时的制膜溶液使用相稳定的温度、优选[制膜时的温度-相分离的温度]的绝对值为10℃以上的相稳定性的溶液。
制备的制膜原液通过湿式纺丝法或干湿式纺丝法,从双重环状结构的中空纤维纺丝喷嘴的外管直接或经空转挤出到凝固浴中,根据需要从纺丝喷嘴的内管同时挤出对制膜原液的溶剂和聚合物为不溶性的芯液,由此通过非溶剂致相分离法使聚苯醚中空纤维膜成型。在这里,芯液和凝固浴使用与制膜原液的溶剂混溶,但对聚苯醚为不溶性的溶剂,例如水、乙二醇等。另外,此时的芯液和凝固浴的温度通常为约-20~60℃,优选为约0~30℃。
得到的聚苯醚中空纤维膜根据需要水洗,接着进行干燥,即从中空丝状物的聚苯醚部分进行水分的除去。干燥只要是聚苯醚中空纤维膜完全干燥的条件,则无特殊限制,通常于约20~80℃,优选于约25~35℃,进行约0.5~4小时左右。另外,也可进行一边对纺丝后的中空纤维膜吹约60~240℃的热风,一边卷绕在线轴上等。在这里,就纺丝后干燥了的中空纤维膜的断面结构而言,在未添加硫的情况下部分地观察到尺寸为数十微米的空隙结构(空隙) (参照比较例1所涉及的图4~6),而在制膜原液中添加硫的情况下不再看到上述空隙结构(参照实施例1所涉及的图1~3)。
干燥了的聚苯醚中空纤维膜在碳化处理前进行不熔化处理。不熔化处理是通过于约150~350℃左右实施约1分钟~2小时左右的加热处理来进行。通过上述不熔化处理,形成在SEM 5000倍左右下观察不到孔这样的致密结构。
另外,关于不熔化处理,除了上述不特别施加应力的状态下的不熔化处理以外,也可通过在对中空纤维膜施加应力的同时,在温度约为250~350℃左右这样的比碳化温度低的温度下实施约0.5~4小时的加热处理来进行。在不熔化处理时对中空纤维膜施加的应力通过在将经纺丝的中空纤维膜卷绕在线轴上时拉伸等来进行,其程度根据中空纤维膜的膜厚、大小而不同,例如对于外径约为400~500μm、内径约为350~450μm的中空纤维膜,施加约0.002~0.005MPa左右的应力。在以往的方法中,通常在空气中在不施加应力、即不施加拉伸方向的力的状态下实施加热,但在本发明中通过在施加应力的同时进行不熔化处理,可在碳中空纤维膜中形成1nm以下的多孔性孔,起到可得到气体透过性优异且分离系数高的中空纤维碳膜这样的优异效果。
需说明的是,在专利文献5~6中,公开了在制膜后一边将膜加热一边拉伸,从而将孔开口或扩大,但在这些方法中在不熔化处理时不进行拉伸。在专利文献5中记载了在纤维素系的膜中通过拉伸来调整10μm以下的孔径,在专利文献6中公开了在结晶性的膜中调整孔径为0.1~1.0μm的孔,但这些发明均局限于将结晶和非晶共存的膜拉伸来调整非晶部位的孔,与如本发明那样通过不熔化处理时的拉伸将碳膜的多孔性孔的孔径调整为1nm以下的发明大不相同。
碳化处理是对前体聚合物中空纤维膜通过例如如下的公知的方法来进行:将前体聚合物中空纤维膜收纳在容器内,在10-4大气压以下(约10Pa以下)的减压下或由氦、氩气、氮气等置换的惰性气体气氛下加热处理。加热条件根据构成前体聚合物的材料的种类、其量等而不同,但通常在上述10-4大气压以下(约10Pa以下)的减压下或惰性气体气氛下,应用约600~800℃、约0.5~4小时这样的条件。
关于得到的中空纤维碳膜,为了进一步提高其分离性能,也可对其表面实施作为公知技术(参照专利文献7等)的化学气相蒸镀(CVD),优选使用丙烯、丁烷、环己烷等烃气体的CVD处理。通过实施上述CVD处理,在纺丝原液中添加硫的碳膜与未添加硫的碳膜相比,可见达成更高分离性等的特征。
实施例
接着,就实施例来说明本发明。
实施例1
由28重量份的聚苯醚树脂(SABIC公司制品PPO646)、0.6重量份的硫(关东化学制品)、71.4重量份的二甲基乙酰胺构成的纺丝原液通过首先在二甲基乙酰胺中溶解硫后,溶解聚苯醚树脂来制备。
将制备的纺丝原液加热至150℃,使用双重环状结构的纺丝喷嘴,将乙二醇作为芯液挤出到水凝固浴中,以15m/分钟的纺丝速度进行干湿式纺丝。然后在60℃的烘箱中干燥,得到外径为1060μm、内径为930μm的多孔性聚苯醚中空纤维膜。将纺丝、干燥后的中空纤维膜的断面SEM放大照片示出于图1~2中。
接着,将得到的中空纤维膜插入全氟烷氧基烷烃树脂(PFA:四氟乙烯-全氟烷基乙烯基醚共聚树脂)制管中,在空气中进行温度为290℃、1小时的加热,实施不熔化处理。进而,将不熔化处理过的中空纤维膜插入石英管中,在氮气氛下进行温度为650℃、1小时的加热,实施碳化处理得到外径为430μm、内径为370μm的中空纤维碳膜。将得到的中空纤维碳膜的断面SEM放大照片示出于图3中。另外,使用得到的碳膜进行气体透过试验。
气体透过试验:将碳膜的一端用环氧树脂粘接而密封,将另一端在Swagelok制的金属垫圈压盖(6LV-4-VCR-3S-6MTB7)的配管部插入10mm,将直到碳膜的插入部位5mm的碳膜与压盖的配管的缝隙用环氧树脂粘接,制备气体分离评价用的小型模件,将其安装在气体分离装置上,在碳膜的外侧以200kPa g的压力流过不同的气体,用质量流量控制器测定管侧透过的气体流量,用得到的气体流量除以膜面积、时间和压力计算气体通过速度。
实施例2
在丙烯气体气氛下,对在实施例1中得到的中空纤维碳膜实施650℃、2分钟的CVD处理。得到的中空纤维碳膜的断面SEM放大照片与实施例1 (图3)相同。另外,对CVD处理后的中空纤维碳膜也进行气体透过试验。
比较例1
使用在实施例1中不使用硫,并将二甲基乙酰胺量变更为72重量份制备的纺丝原液进行干湿式纺丝,在干燥后得到外径为800μm、内径为650μm的多孔性聚苯醚中空纤维膜,并且在不熔化处理和碳化处理后得到外径为435μm、内径为375μm的中空纤维碳膜。将纺丝、干燥后的中空纤维膜的断面SEM放大照片示出于图4~5中,并且将不熔化、碳化处理后的中空纤维碳膜的断面SEM放大照片示出于图6中。
比较例2
在丙烯气体气氛下,对在比较例1中得到的中空纤维碳膜实施650℃、2分钟的CVD处理。得到的中空纤维碳膜的断面SEM放大照片与比较例1 (图6)相同。另外,对CVD处理后的中空纤维碳膜也进行气体透过试验。
将以上各实施例和比较例中得到的气体透过试验的结果与分离系数一起示出于下面的表1中,并且将气体分子直径与气体透过速度的关系作曲线而得的曲线图示出于图7(▲:实施例1,●:实施例2,△:比较例1,○:比较例2)中。
实施例3
将在实施例1中制备的纺丝原液加热至150℃,使用双重环状结构的纺丝喷嘴,将乙二醇作为芯液挤出到水凝固浴中,以15~20m/分钟的纺丝速度进行干湿式纺丝。然后吹220℃的热风,在干燥的同时卷绕在线轴上,得到外径为450μm、内径为395μm的多孔性中空纤维膜。
接着,在对中空纤维膜施加0.004MPa的应力的同时,在空气中进行温度为320℃、1小时的加热,实施不熔化处理。进而,将不熔化处理过的中空纤维膜插入石英管中,在氮气氛下进行温度为700℃、45分钟的加热,实施碳化处理,最后在氮和丙烯气体气氛下实施温度为700℃、5分钟的CVD处理,得到外径为265μm、内径为220μm的多孔性聚苯醚中空纤维碳膜。使用得到的碳膜,进行与上述相同的气体透过试验。
实施例4
在实施例3中,将在不熔化处理时对中空纤维膜施加的应力变更为0.005MPa,得到外径为200μm、内径为165μm的多孔性聚苯醚中空纤维膜。
实施例5
在实施例3中,不熔化处理中不对中空纤维膜施加应力,而通过在空气中温度为320℃、1小时的加热来进行,得到外径为315μm、内径为270μm的多孔性聚苯醚中空纤维膜。
比较例3
在实施例3中,将不熔化处理时对中空纤维膜施加的应力变更为0.006MPa,结果中空纤维膜断裂,无法得到多孔性聚苯醚中空纤维膜。
以上实施例3~5中得到的结果与不熔化处理时对中空纤维膜施加的应力和中空纤维膜的膜厚一起示出于下面的表2中。
产业上的可利用性
本发明所涉及的碳膜可有效地用于从氢或氦这样的有益的低分子气体与甲烷或甲苯等有机气体混合的气体只取出氢或氦的用途,或蒸气分离、膜面蒸馏用的膜等。另外,由于耐热性、耐化学药品性优异,所以也可用于有机膜无法应用的用途。
Claims (6)
1.碳膜用制膜原液,在制膜原液中,达到15~40重量%的浓度的量的聚苯醚和在该聚苯醚和硫的总重量中达到0.1~5.0重量%的比例的量的硫溶解于可溶解它们的溶剂中。
2.权利要求1所述的碳膜用制膜原液,其进一步添加使用有机过氧化物、酚醛树脂交联剂或醌二肟交联剂。
3.中空纤维碳膜的制备方法,其中,使用双重环状喷嘴,通过湿式或干湿式纺丝法将权利要求1所述的碳膜用制膜原液成型为中空状,在空气中于150~350℃加热从而不熔化处理后,在惰性气氛或真空中于600~800℃加热来进行碳化处理。
4.权利要求3所述的中空纤维碳膜的制备方法,其中,将通过湿式或干湿式纺丝法成型为中空状的产品一边在0.002~0.005MPa的应力下拉伸,一边在空气中加热从而不熔化处理。
5.中空纤维碳膜,其通过权利要求3或4所述的制备方法制备。
6.权利要求5所述的中空纤维碳膜,其中,进一步对表面实施了使用烃气体的化学气相蒸镀。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014221063 | 2014-10-30 | ||
JP2014-221063 | 2014-10-30 | ||
JP2015079206 | 2015-04-08 | ||
JP2015-079206 | 2015-04-08 | ||
PCT/JP2015/078773 WO2016067900A1 (ja) | 2014-10-30 | 2015-10-09 | 炭素膜用製膜原液およびこれを用いた炭素中空糸膜の製造方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN107106995A true CN107106995A (zh) | 2017-08-29 |
Family
ID=55857241
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201580059047.8A Pending CN107106995A (zh) | 2014-10-30 | 2015-10-09 | 碳膜用制膜原液及使用其的碳中空纤维膜的制备方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US10150085B2 (zh) |
EP (1) | EP3228382A4 (zh) |
JP (1) | JP6358337B2 (zh) |
KR (1) | KR101960794B1 (zh) |
CN (1) | CN107106995A (zh) |
CA (1) | CA2963222A1 (zh) |
WO (1) | WO2016067900A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115362288A (zh) * | 2020-03-31 | 2022-11-18 | 东洋纺株式会社 | 不熔融化聚苯醚纤维、不熔融化聚苯醚成形体、碳纤维、活性碳纤维、碳纤维成型体、活性碳纤维成型体及其制造方法 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6729012B2 (ja) * | 2016-06-07 | 2020-07-22 | 東洋紡株式会社 | 中空糸炭素膜の製造方法 |
US11517857B2 (en) | 2017-08-14 | 2022-12-06 | Dow Global Technologies Llc | Method to make carbon molecular sieve hollow fiber membranes |
EP4083327A1 (de) | 2021-04-29 | 2022-11-02 | RTG Rammtechnik GmbH | Tiefbaumaschine |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3311587A (en) * | 1965-03-10 | 1967-03-28 | Gen Electric | Polyphenylene oxides extended with elemental sulfur |
CN1044122A (zh) * | 1988-12-22 | 1990-07-25 | 普罗格特-甘布尔公司 | 着色稳定的漂白活化剂挤出物 |
CN1093299A (zh) * | 1993-03-23 | 1994-10-12 | 罗坦工业有限公司 | 通过化学碳气相沉积改进碳膜选择性的方法 |
CN101497704A (zh) * | 2009-02-25 | 2009-08-05 | 厦门大学 | 一种耐高温、超亲水聚苯乙烯多孔膜材料及其制备方法 |
CN101754796A (zh) * | 2007-08-02 | 2010-06-23 | 独立行政法人产业技术总合研究所 | 中空纤维碳膜及其制造方法 |
JP2013063415A (ja) * | 2011-09-20 | 2013-04-11 | Toyobo Co Ltd | 中空糸炭素膜、分離膜モジュールおよび中空糸炭素膜の製造方法 |
CN103370123A (zh) * | 2011-02-02 | 2013-10-23 | Nok株式会社 | 用于碳膜的成膜原液及使用其制备碳中空纤维膜的方法 |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3735559A (en) * | 1972-02-02 | 1973-05-29 | Gen Electric | Sulfonated polyxylylene oxide as a permselective membrane for water vapor transport |
JPS6328406A (ja) | 1986-07-21 | 1988-02-06 | Asahi Medical Co Ltd | 網目状多孔質中空糸膜 |
JPH0638899B2 (ja) | 1985-07-31 | 1994-05-25 | 旭化成工業株式会社 | 膜処理法 |
US5364454A (en) * | 1993-06-30 | 1994-11-15 | Praxair Technology, Inc. | Fluid separation composite membranes prepared from sulfonated aromatic polymers in lithium salt form |
US5348569A (en) * | 1993-06-30 | 1994-09-20 | Praxair Technology, Inc. | Modified poly(phenylene oxide) based membranes for enhanced fluid separation |
US5356459A (en) * | 1993-06-30 | 1994-10-18 | Praxair Technology, Inc. | Production and use of improved composite fluid separation membranes |
US5635067A (en) * | 1995-03-14 | 1997-06-03 | Praxair Technology, Inc. | Fluid separation membranes prepared from blends of polyimide polymers |
US5989742A (en) * | 1996-10-04 | 1999-11-23 | The Research Foundation Of State University Of New York | Blend membranes based on sulfonated poly(phenylene oxide) for enhanced polymer electrochemical cells |
US6103414A (en) * | 1995-12-28 | 2000-08-15 | The Research Foundation Of State University Of The New York | Blend membranes based on sulfonated poly(phenylene oxide) for polymer electrochemical cells |
US6248469B1 (en) * | 1997-08-29 | 2001-06-19 | Foster-Miller, Inc. | Composite solid polymer electrolyte membranes |
JP2000185212A (ja) | 1998-12-22 | 2000-07-04 | Ube Ind Ltd | パーフルオロ化合物ガスの分離回収方法および装置 |
JP3607862B2 (ja) * | 2000-09-29 | 2005-01-05 | 株式会社日立製作所 | 燃料電池 |
US6681648B1 (en) * | 2001-04-04 | 2004-01-27 | The Regents Of The University Of California | Meniscus membranes for separations |
CN101039744B (zh) * | 2004-08-13 | 2010-05-05 | 麦克马斯特大学 | 包含非交联的胶凝聚合物的复合材料 |
DE102007058320A1 (de) * | 2006-12-23 | 2008-06-26 | Evonik Degussa Gmbh | Membranen zur Trennung von Gasen |
JP5206066B2 (ja) * | 2007-03-28 | 2013-06-12 | Jnc株式会社 | 重合性液晶組成物 |
JP4998929B2 (ja) * | 2009-02-16 | 2012-08-15 | 大陽日酸株式会社 | ガス精製方法 |
JP5966298B2 (ja) | 2011-09-28 | 2016-08-10 | 東洋紡株式会社 | 中空糸炭素膜の製造方法 |
JP5906675B2 (ja) | 2011-11-02 | 2016-04-20 | 東洋紡株式会社 | 中空糸炭素膜、分離膜モジュールおよび中空糸炭素膜の製造方法 |
EP2977350B1 (en) * | 2013-03-22 | 2019-12-11 | Toray Industries, Inc. | Porous carbon material, precursor for porous carbon material, process for producing precursor for porous carbon material, and process for producing porous carbon material |
CA2969199A1 (en) * | 2014-12-12 | 2016-06-16 | Nok Corporation | Method for producing a hollow fiber carbon membrane |
-
2015
- 2015-10-09 KR KR1020177012109A patent/KR101960794B1/ko active IP Right Grant
- 2015-10-09 WO PCT/JP2015/078773 patent/WO2016067900A1/ja active Application Filing
- 2015-10-09 EP EP15856046.6A patent/EP3228382A4/en not_active Withdrawn
- 2015-10-09 CA CA2963222A patent/CA2963222A1/en not_active Abandoned
- 2015-10-09 JP JP2016556484A patent/JP6358337B2/ja active Active
- 2015-10-09 CN CN201580059047.8A patent/CN107106995A/zh active Pending
- 2015-10-09 US US15/515,940 patent/US10150085B2/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3311587A (en) * | 1965-03-10 | 1967-03-28 | Gen Electric | Polyphenylene oxides extended with elemental sulfur |
CN1044122A (zh) * | 1988-12-22 | 1990-07-25 | 普罗格特-甘布尔公司 | 着色稳定的漂白活化剂挤出物 |
CN1093299A (zh) * | 1993-03-23 | 1994-10-12 | 罗坦工业有限公司 | 通过化学碳气相沉积改进碳膜选择性的方法 |
CN101754796A (zh) * | 2007-08-02 | 2010-06-23 | 独立行政法人产业技术总合研究所 | 中空纤维碳膜及其制造方法 |
CN101497704A (zh) * | 2009-02-25 | 2009-08-05 | 厦门大学 | 一种耐高温、超亲水聚苯乙烯多孔膜材料及其制备方法 |
CN103370123A (zh) * | 2011-02-02 | 2013-10-23 | Nok株式会社 | 用于碳膜的成膜原液及使用其制备碳中空纤维膜的方法 |
JP2013063415A (ja) * | 2011-09-20 | 2013-04-11 | Toyobo Co Ltd | 中空糸炭素膜、分離膜モジュールおよび中空糸炭素膜の製造方法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115362288A (zh) * | 2020-03-31 | 2022-11-18 | 东洋纺株式会社 | 不熔融化聚苯醚纤维、不熔融化聚苯醚成形体、碳纤维、活性碳纤维、碳纤维成型体、活性碳纤维成型体及其制造方法 |
CN115362288B (zh) * | 2020-03-31 | 2023-11-03 | 东洋纺Mc株式会社 | 不熔融化聚苯醚纤维、不熔融化聚苯醚成形体、碳纤维、活性碳纤维、碳纤维成型体、活性碳纤维成型体及其制造方法 |
Also Published As
Publication number | Publication date |
---|---|
JP6358337B2 (ja) | 2018-07-18 |
US20170296978A1 (en) | 2017-10-19 |
US10150085B2 (en) | 2018-12-11 |
EP3228382A4 (en) | 2018-07-11 |
WO2016067900A1 (ja) | 2016-05-06 |
EP3228382A1 (en) | 2017-10-11 |
JPWO2016067900A1 (ja) | 2017-08-31 |
KR101960794B1 (ko) | 2019-03-21 |
KR20170077147A (ko) | 2017-07-05 |
CA2963222A1 (en) | 2016-05-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107106995A (zh) | 碳膜用制膜原液及使用其的碳中空纤维膜的制备方法 | |
CN106999867A (zh) | 碳中空纤维膜的制备方法 | |
JP5832907B2 (ja) | ポリオレフィン微多孔膜の製造方法 | |
JP6054318B2 (ja) | エチレン/エタン分離のためのポリイミド系炭素分子ふるい膜 | |
CN108530673B (zh) | 一种线型聚酰亚胺气凝胶及其制备方法 | |
JP5966298B2 (ja) | 中空糸炭素膜の製造方法 | |
Ding et al. | Effects of annealing on structure and deformation mechanism of isotactic polypropylene film with row‐nucleated lamellar structure | |
Ren et al. | Preparation and investigation of reinforced PVP blend membranes for high temperature polymer electrolyte membranes | |
Itta et al. | Effect of dry/wet-phase inversion method on fabricating polyetherimide-derived CMS membrane for H2/N2 separation | |
Hou et al. | High-performance carbon molecular sieving membrane derived from a novel hydroxyl-containing polyetherimide precursor for CO2 separations | |
JP2018134611A (ja) | 中空糸炭素膜の製造方法 | |
Yu et al. | Fabrication and characterization of a novel Nafion‐PTFE composite hollow fiber membrane | |
JP5289790B2 (ja) | カーボン膜を備える分離膜エレメントの製造方法 | |
TW201908003A (zh) | 流體分離用碳膜及其製造方法 | |
JP5772275B2 (ja) | 中空糸炭素膜の製造方法 | |
CN104681833B (zh) | 一种纳米陶瓷纤维管燃料电池质子交换膜及制备方法 | |
JP2016083612A (ja) | 炭素膜用製膜原液およびこれを用いた中空糸炭素膜の製造方法 | |
Zhang et al. | Innovative all-organic dielectric composite for dielectric capacitor with great energy storage performance based on thermodynamic compatibility | |
JP2010215417A (ja) | ガス分離用セラミック薄膜の製造方法 | |
JPS6226122B2 (zh) | ||
CN116651233A (zh) | 一种低温炭分子筛膜的制备方法 | |
CN116157561A (zh) | 碳中空纤维膜 | |
Chen et al. | Fabrication of high-flux defect-free hollow fiber membranes derived from a phenolphthalein-based copolyimide for gas separation | |
JP2010144299A (ja) | 黒鉛化繊維及びその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170829 |